Heterocyclic 2,3-dihydrobenzofuran herbicides

ABSTRACT

This invention pertains to novel heterocyclic 2,3-dihydrobenzofuran and chromane compounds, including stereoisomers, agriculturally suitable composition containing them, and their use as broad spectrum herbicides.

RELATED APPLICATION

This is a continuation in part of copending application 06/943,365, filed Dec. 10, 1986, now abandoned.

BACKGROUND OF THE INVENTION

Novel heterocyclic 2,3-dihydrobenzofuran and chromane herbicides show utility as agrichemicals.

EP-A-170191, published Feb. 5, 1986 discloses herbicidal compounds of the following formula. ##STR1## where X is H, Cl or F;

n is 0 or 1;

R₁ is H, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, or alkoxyalkoxyalkyl; and

R₂ and R₃ are H, halogen, alkyl or phenyl.

U.S. Pat. No. 4,431,822 (filed March 23, 1982) discloses compounds of the following formula as herbicides. ##STR2##

U.S. Pat. No. 4,406,910 filed May 6, 1982 discloses compounds of the following formula as pesticides (insecticides). ##STR3## wherein R is alkyl of 1-2 carbons or propynyl;

R¹ is H or alkyl of 1-3 carbons;

R² is alkyl of 1-3 carbons; and

R³ is H, Cl, Br or alkyl of 1-3 carbons.

U.S. Pat. No. 4,670,046 discloses compounds of the following formula as herbicides. ##STR4##

U.S. Pat. No. 4,536,209 discloses compounds of the following formula as herbicides. ##STR5## wherein in part X and Y are H or halogen;

A is ##STR6## and; B is CO₂ R³

JP 60,233,075 discloses compounds of the following formula as herbicides. ##STR7## wherein in part R is Cl or Br;

R₁ is H, alkyl or Ph; and

R₂ is OR³, SR⁴ or NR⁵ R⁶.

U.S. Pat. No. 4,437,877 discloses compounds of the following formula as herbicides. ##STR8## wherein in part R is alkyl, allyl or propargyl.

U.S. Pat. No. 4,452,981 discloses compounds of the following formula as herbicides. ##STR9## wherein in part R is alkyl, allyl or propargyl.

JP 59,204,181 discloses compounds of the following formula as herbicides. ##STR10##

U.S. Pat. No. 4,599,104 discloses compounds of the following formula as herbicides. ##STR11## wherein in part R is H, alkoxy alkynyloxy or alkenyloxy.

U.S. Pat. No. 4,670,043 discloses compounds of the following formula as herbicides. ##STR12## wherein in part Y is O; and

R is alkyl, alkenyl or alkynyl.

EP-A 142,769 discloses compounds of the following formula as herbicides. ##STR13##

U.S. Pat. No. 3,385,862 discloses a compound of the following formula as a herbicide. This compound is known as Ronstar™. ##STR14##

EP-A 161,304 discloses compounds of the following formula as herbicides. ##STR15## wherein in part Z is alkoxy.

DE 3,514,057 discloses compounds of the following formula as herbicides. ##STR16##

PCT publication WO 86/00072 discloses compounds of the following formula as herbicides. ##STR17## wherein in part Z is QR;

Q is O or S; and

R is alkyl.

JP 61,40,261 discloses compounds of the following formula as herbicides ##STR18## wherein in part R, and R₂ are halogen; and

R is H and haloalkyl; and

U.S. Pat. No. 4,213,773 discloses compounds of the following formula as herbicides. ##STR19## wherein in part X and Y are halogen;

Z is H or halogen;

V is OR₁ ; and

R₁ is alkyl, alkenyl or alkynyl.

The presence of undesired vegetation causes substantial damage to useful crops, especially agricultural products that satisfy man's basic food needs, such as soybeans, barley, wheat, and the like. The current population explosion and concomitant world food shortage demand improvements in the efficiency of producing these crops. Prevention or minimizing the loss of a portion of valuable crops by killing, or inhibiting the growth of undesired vegetation is one way of improving this efficiency.

A wide variety of materials useful for killing, or inhibiting (controlling) the growth of undesired vegetation is available; such materials are commonly referred to as herbicides. The need exists, however, for still more effective herbicides that destroy or retard weeds without causing significant damage to useful crops.

SUMMARY OF THE INVENTION

This invention pertains to compounds of formula I including stereoisomers, agriculturally suitable compositions containing them, and their use as broad spectrum herbicides. ##STR20## wherein, R is H, Cl, F, C₁ -C₂ alkyl or C₁ -C₃ alkoxy;

R₁ is H, F, Cl, Br, CH₃, OCH₃, CN, CF₃, OCF₃ or OCF₂ H;

X¹ is O or S;

R₂ is H, CH₃ or CH₂ CH₃ ;

R₃ is H, C₁ -C₄ haloalkyl, CR₂ R₇ CN, CN, CR₂ R₄ R₇, COCl, COR₄, C(NOR₆)R₂, CO₂ R₄, CONR₄ R₂, CHR₂ OH, CO₂ (CH₂)₂ Si(CH₃)₃, CONR₂ SO₂ CH₃, CHR₂ CO₂ R₄, CONHCH(CH₃)CONHCH(CH₃)CO₂ CH₃, CHR₂ COR₄, CHR₂ OSO₂ (C₁ -C₄ alkyl), CHR₂ OC(O)R₄, CHR₂ OC(O)N(R₂)₂, CHR₂ OC(O)N(R₂)OCH₃, CHR₂ OC(O)N(R₂)Ph, HC═CH₂ or C.tbd.CH;

R₄ is H, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₂ -C₆ alkenyl, C₃ -C₆ alkynyl, C₂ -C₄ haloalkenyl, phenyl, C₁ -C₄ alkylphenyl, C₃ -C₆ alkoxycarbonylalkyl or (CH₂ CH₂ O)_(b) R₂ ;

b is 1 to 6;

m and n are independently 1 or 2;

J is ##STR21## wherein X and Y each is O or S;

Z is C or N;

W is S or SO₂ ;

R₆ is H, C₁ -C₅ alkyl, allyl, propargyl, benzyl, CH₂ CO₂ CH₃ or CH₂ CO₂ CH₂ CH₃ ;

R₇ is H or CH₃ ;

R₈ is Cl, C₁ -C₄ alkyl or C₁ -C₄ haloalkyl;

R₉ is Cl, F, Br, CH₃, CN, OCH₃, SCH₃ or SO₂ CH₃ ; and

R₁₀ is C₁ -C₄ alkyl or C₁ -C₄ haloalkyl.

Preferred compounds are:

1. Compounds of formula 1 wherein

R and R₁ are H or halogen; and

R₂ is H.

2. Compounds of Preferred 1 wherein

R₄ is H, C₁ -C₃ alkyl, C₁ -C₂ haloalkyl, allyl, propargyl, C₃ haloalkenyl, C₃ -C₄ alkoxycarbonylalkyl or (CH₂ CH₂ O)_(b) R₂ ; and

b is 1 or 2.

3. Compounds of Preferred 2 wherein

R₃ is H, CN, C₁ -C₂ haloalkyl, CR₂ R₇ R₄, CR₂ R₇ CN, CH═CH₂, C.tbd.CH, COCl, COR₄, C(NOR₆)R₂, CO₂ R₄, CH₂ COR₄, CH₂ CO₂ R₄, CH₂ OC(O)R₄ or CH₂ OC(O)N(CH₃)₂ ; and

R₆ is H, allyl, C₁ -C₃ alkyl or CH₂ CO₂ CH₂ CH₃.

4. Compounds of Preferred 3 wherein

J is J-2, J-3, J-4, J-7, J-9, J-10, J-11, J-12 or J-15; and

X and Y are O.

5. Compounds of Preferred 4 wherein

R₉ is Cl or Br; and

R₈ is CH₃.

6. Compounds of Preferred 5 wherein

J is J₂ or J₁₀ ; and

X¹ is O.

7. Compounds of Preferred 6 wherein

J is in the 5 position;

R is F or Cl and in the 4 position; and

R₁ is Cl or Br and in the 2 position.

8. Compounds of Preferred 6 wherein

J is in the 4 position;

R is F or Cl and is in the 3 position; and

R₁ is H.

9. Compounds of Preferred 6 wherein

J is in the 3 position;

R is F or Cl and is in the 4 position; and

R₁ is H.

10. Compounds of Preferred 6 wherein

J is in the 2 position;

R is F or Cl and is in the 3 position; and

R₁ is Cl or Br and is in the 5 position.

11. Compounds of Preferred 7 wherein

J is J-2.

12. Compounds of Preferred 7 wherein

J is J-10 and

n is 1.

13. Compounds of Preferred 11 wherein

m is 2.

14. Compounds of Preferred 12 wherein

m is 1.

15. A method-of-use of the compounds of Preferred 14 for the control of nightshade in cereal crops.

Specifically Preferred

Specifically preferred for reasons of ease of synthesis and/or biological activity are

2-BENZOFURANMMETHANOL-7-CHLORO-5-FLUORO-4-(2,3,4,5,6,7-HEXAHYDRO-1,3-DIOXO-1H-ISOINDOL-2-yl)-2,3-DIHYDRO-α-METHYL, ACETATE.

((1,2,4))-TRIAZOLO((4,3-A))PYRIDIN-3(2H)-ONE, 2-(5,7-DICHLORO-2,3-DIHYDRO-2-METHYL-4-BENZOFURANYL)-5,6,7,8-TETRAHYDRO-.

2-BENZOFURANCARBOXYLIC ACID-7-CHLORO-5-FLUORO-4-(2,3,4,5,6,7-HEXAHYDRO-1,3-DIOXO-1H-ISOINDOL-2-YL)-2,3-DIHYDRO-, METHYL ESTER.

In these compounds, each aliphatic moiety can be either straight chain or branched-chain. "Halogen" is bromine, chlorine and fluorine.

DETAILED DESCRIPTION OF THE INVENTION

Compounds of formula I wherein J is J-1, J-2 or J-10, X and Y are oxygen, m is one, n is one or two, R₂ is hydrogen, methyl or ethyl and R₃ is CHR₄ R₇, can be prepared by cyclizing the appropriate J-1, J-2 and J-10 allyl phenols of formula II as outlined in Scheme I. ##STR22##

The cyclization can be effected by one or more of three general methods:

(a) thermal: the phenol precursor II, optionally in a solvent such as xylene, is heated at 150°-250° C.;

(b) acid catalyzed: refluxing a solution of the phenol precursor II in an inert solvent, such as xylene, containing a catalytic amount of p-toluenesulfonic acid (PTSA).

(c) free-radical: treating the phenol precursor II with hydrogen bromide in the presence of a peroxide.

Such methods are described by L. I. Smith, Chemical Reviews, page 287, et seq., 1940.

Depending on the nature of substituents R₂, R₄, and R₇ in II, the above cyclization process may produce varying amounts of I in which m is one and/or two.

In addition to the methods described above, compounds of the subclass of formula I wherein J is J-1, J-2 or J-10, X is oxygen, m is one or two, n is one or two, R₂ is hydrogen, methyl or ethyl, and R₃ is hydrogen, CR₂ R₇ CN, CN, CR₂ R₄ R₇, COR₄, C(NOR₆)R₂, CO₂ R₄, CONR₄ R₂, CHR₂ CO₂ R₄, CHR₂ C(O)R₄, CHR₂ OC(O)R₄, CHR₂ OC(O)N(R₂)₂, CH═CH₂ or C.tbd.CH, may be prepared by dehydration of the precursor III. A preferred method is by refluxing a mixture of III with PTSA in a suitable inert solvent such as xylene. Alternatively, contacting III with a mixture of triphenylphosphine and diethylazodicarboxylate in an inert solvent such as tetrahydrofuran at about 0° C. to 25° C., according to the method of R. G. Salomon et al., J. Org. Chem. 52, 1072 (1987), produces I, where m=2. This is outlined in Scheme II. ##STR23##

The intermediate diol derivative III, where m is 2, is produced from the allyl phenol precursor IV by treatment of IV, where R₃ is as previously defined, with borane or 9-BBN (9-borabicyclo[3.3.1]nonane) in an inert solvent such as tetrahydrofuran at 0° C. to 70° C. The resultant organoborane is oxidized with a basic hydrogen peroxide solution from 0° C. to 55° C. following the general procedures described by H. C. Brown, Organic Synthesis via Boranes, Wiley Interscience, New York, 1975; H. C. Brown and C. G. Scouten, J. Org. Chem., 38, 4092 (1973). This is outlined in Scheme III. ##STR24##

Compounds of formula I wherein J is as previously described also can be prepared by treating phenol II with a moderate stoichiometric excess of an epoxidizing agent such as peracetic acid, m-chloroperoxybenzoic acid or a like reagent, in an inert solvent such as 1,2-dichloroethane at a temperature of about 0°-80° C., to form an epoxide of formula V. ##STR25##

The reaction preferably is conducted by refluxing the mixture of phenol, epoxidizing agent and solvent until the reaction is complete, then treating the mixture with an aqueous solution of sodium sulfite until no reaction is obtained on starch/potassium iodide paper.

The epoxide V may spontaneously cyclize at room temperature, or it may be cyclized by (a) an acid catalyst (PTSA) and/or like protic catalyst in an inert solvent such as 1,2-dichloroethane, or (b) a basic catalyst, such as sodium hydride or a tertiary amine, in an inert solvent such as tetrahydrofuran (THF) or N,N-dimethylformamide (DMF) at a temperature of about 0° C. to 100° C. The products are characterized by formula VI, as outlined in Scheme IV.

The phenol precursors II and IIA can be prepared by Claisen rearrangement of the appropriate substituted compounds of formula VII as outlined in Scheme V. ##STR26##

When R¹ is hydrogen at position two, the product is ordinarily a mixture of the two isomeric forms IIA an II. When R¹ is other than hydrogen, only the isomeric form II is obtained. The rearrangement is effected by heating the allyloxyphenyl precursor VII at a moderately elevated temperature--for example a temperature within the range of from about 120° C. to about 250° C. The precursor VII per se (i.e., neat) may be used or it may be in solution in a suitable inert solvent, such as N,N-dimethylaniline. Alternatively, the rearrangement can be effected at about 0° C. to room temperature by employing a Lewis acid catalyst, such as boron trichloride, in an inert solvent, such as methylene chloride, following a procedure described by R. Barner, et al., Helv. Chim. Acta, 56, 14 (1973). It is to be noted that in some cases, at least, when the precursor is heated at a temperature within the upper portion of the indicated range--for example, above about 200° C.--cyclization may occur, in addition to the rearrangement.

Generally speaking, mixtures of the benzofuran and benzopyran will be obtained from all of the cyclization procedures, the relative proportions of the two materials depending upon the character of the moieties R₂, R₄ and R₇ and the method, (a), (b), (c), or epoxidation, followed by treatment with acid or base to effect the cyclization.

Allyloxyphenyl precursors VII can be prepared by treating a solution of the appropriate substituted compounds of formula VIII with appropriate allyl halides IX. ##STR27## The reaction is best run with the bromide at about room temperature to 100° C. in an inert solvent (such as acetone, acetonitrile or N,N-dimethylformamide) in the presence of potassium carbonate.

Precursor phenols VIII can be prepared by conventional procedures, as by heating a mixture of an appropriate phthalic or 3,4,5,6-tetrahydrophthalic anhydride and an appropriate aniline X ##STR28## in acetic acid, toluene or xylene. The reaction can be catalyzed in xylene or toluene by an amine such as triethylamine or DBU (1,8-diazabicyclo[5.4.0]undec-7-ene). Procedures for preparing such precursor phenols VIII are well known, being described inter alia, in U.S. Pat. No. 4,452,981, European patent application No. 61,741 and United Kingdom patent application No. 2,046,754, and in references cited therein.

Alternatively, allyloxyphenyl precursors VII can be prepared by heating a mixture of an appropriate anhydride, such as phthalic or 3,4,5,6-tetrahydrophthalic anhydride, and an appropriate allyloxyaniline of formula XI ##STR29## in acetic acid, these anilines being prepared from the corresponding allyloxynitrobenzenes (as by treating the nitrobenzene with stannous chloride in a solvent such as ethyl acetate), the allyloxynitrobenzenes being prepared by treating the corresponding nitrophenols with the appropriate allyl halides IX as described earlier in Scheme VI.

The thio-analogs, where J is as defined in the 5-position, R₂ is hydrogen, R is fluorine and is in the 4-position and R₁ is chlorine and is in the 2-position, may be prepared as described below. The allylphenol XII when treated with N,N-dimethylthiocarbamoyl chloride in the presence of DABCO (1,4-diazabicyclo[2.2.2]octane) in DMF at about 0° C. to room temperature affords thiocarbamate XIII as outlined in Scheme VII. ##STR30##

Thermal rearrangement of XIII may be effected in a suitable inert solvent such as o-dichlorobenzene at 150°-250° C. to produce carbamate derivative XIV. Cyclization of XIV with an anhydrous acid, such as hydrogen bromide in acetic acid at refluxing temperatures affords XV as outlined in Scheme VIII. ##STR31##

Treatment of XIV with N-bromosuccinimmide in a mixture of carbon tetrachloride and chloroform at about 0° C. to room temperature affords the bromide XVI. Reaction of XVI with a mixture of acetic acid and sodium acetate at refluxing temperature gives the acetate derivative XVII, as outlined in Scheme IX. ##STR32## Hydrolysis of XVII, for example with refluxing aqueous ethanolic hydrogen chloride of treatment of XVI with dimethylsulfoxide containing traces of moisture at about 80°-110° C. results in the formation of the alcohol derivative XVIII as outlined in Scheme X. ##STR33## Oxidation of XVIII, for example with a mixture consisting of pyridinium dichromate, acetic anhydride, and tert-butanol in an inert solvent as previously described would afford the tert-butyl ester XIX, where R₄ =C(CH₃)₃. Hydrolysis of the tert-butyl ester may be achieved for example with trifluoroacetic acid as described above to produce the carboxylic acid XX, where R₄ =H. Esterification of XX with diazomethane in methylene chloride at 0° C. would afford methyl ester XXI, where R₄ =CH₃. This is outlined in Scheme XI. ##STR34##

Compounds of Formula I wherein R₃ is one of the defined functional moieties can be prepared by treatment of an appropriate compound of Formula I by conventional procedures and reagents, as illustrated in the Examples, hereinafter. Thus, various subclasses of compounds of formulae I can be prepared as follows from precursors wherein R₃ is --CH(R₂)--OH.

Compounds wherein R₃ is --CH(R₂)--OH, (1) upon treatment with a carboxylic acid anhydride or acid chloride produce an ester, CHR₂ OC(O)R₄ ; (2) by treatment of the alcohol with an alkylsulfonyl chloride produce a sulfonate. CHR₂ OSO₂ (C₁ -C₄ alkyl); or (3) treatment of the alcohol with cyanic acid, an isocyanate, or a carbamoyl chloride produce carbamates, CHR₂ OC(O)N(R₂)₂, CHR₂ OC(O)N(R₂)OCH₃, and CHR₂ OC(O)N(R₂)Ph.

Compounds wherein R₃ is --C(R₂)═NO(R₆) also may be prepared by conventional procedures: oxidation of an appropriate compound of Formula I wherein R₃ is --CH(R₂)OH with a mixture of oxalyl chloride, dimethylsulfoxide and triethylamine, according to the procedure reviewed by A. J. Mancuso and D. Swern, Synthesis, 165 (1981), to form an aldehyde to ketone wherein R₃ is --C(O)--(R₂), which can be subsequently treated with a hydroxylamine to form the oxime, (--C(R₂)═NOR₆).

The aldehyde, upon treatment with methylene triphenylphosphorane in a suitable inert solvent such as dimethylsulfoxide or benzene at about 0° C. to 70° C., produces the olefin wherein R₃ is CH═CH₂. Such Wittig-type reactions are reviewed in A. Maercker, Org. React., 14, 270 (1965) and H. House, "Modern Synthetic Reactions", Benjamin, Menlo Park, CA, 1972, pp. 682-709.

Compounds wherein R₃ is --C(O)--O(R₄), --C(O)N(R₄)(R₂), --C(O)Cl or --CN can be prepared by conventional treatment of an alcohol, --CH(R₂)--OH where R₂ is hydrogen, with Jones' reagent or pyridinium dichromate to give the corresponding carboxylic acid, R₃ is --C(O)OH. Alternatively, oxidation of the alcohol, where R₂ is hydrogen, with pyridinium dichromate in the presence of tert-butanol and acetic anhydride in an inert solvent such as methylene chloride at about 0° C. to 40° C. as described by E. J. Corey and B. Samuelsson, J. Org. Chem., 49, 4735 (1984), affords the tertiary butyl ester, R₃ =CO₂ C(CH₃)₃. Hydrolysis of the tert-butyl ester with trifluoroacetic acid at about 0° C. to 50° C. provides the carboxylic acid, R₃ is CO₂ H. The carboxylic acid which can be converted to a salt, or to an ester CO₂ R₄, or to an amide --C(O)N(R₄)(R₂ ), by treatment of the acid with thionyl chloride to form the acid chloride (R₃ =-C(O)Cl) and treatment of the acid chloride with an appropriate alcohol R₄ --OH or amine H--N(R₄)(R₂), respectively. Treatment of the acid chloride with ammonia produces the unsubstituted amide, which is dehydrated by conventional procedures to the nitrile, R₃ =-CN. Treatment of the acid chloride with lithium dianion of methyl phenyl sulfone in tetrahydrofuran (THF), conversion of the resultant intermediate to the corresponding O,O-diphenylenol phosphate derivative, and reduction with sodium in a liquid ammonia-THF solution affords the acetylene derivative, where R₃ is C.tbd.CH. Such procedures are described by P. A. Bartlett et al., J. Am. Chem. Soc., 100, 4852 (1978).

Compounds wherein R₃ is C(R₂)(R₇)CN are prepared by treating an appropriate compound of Formula I wherein R₃ is --CH(R₂)OH, with mesyl chloride to form the mesylate, and treating the mesylate with potassium cyanide.

Compounds wherein R₃ is C₁ -C₄ haloalkyl are prepared by treating an appropriate compound of Formula I wherein R₃ is --CH(R₂)OH with a carbon tetrahalide derivative in the presence of triphenylphosphine in an inert solvent such as methylene chloride following the procedures of P. J. Kocienski et al., J. Org. Chem., 42, 353 (1977).

Compounds of Formula I can also be prepared by the following general methods:

J=J-1, J-2 in addition to the methods already described, these compounds can be prepared by treating an appropriate phthalic or tetrahydrophthalic anhydride with an appropriate aniline, by fusing the two reagents at a temperature of 120°-220° C., or by refluxing a mixture of the reagents in a solvent such as acetic acid, toluene or xylene. The reaction can be catalyzed in xylene or toluene by an amine such as triethylamine or DBU (1,8-diazabicyclo[5.4.0]undec-7-ene). The products wherein one or both of X and Y is (are) sulfur can be prepared by treating (i.e., thionating) a product wherein X and y are both oxygen with phosphorus pentasulfide or Lawesson's Reagent (2,4-bis-(4-methoxyphenyl)-1,3-dithia-2,4-diphosphetane-2,4-disulfide), in an inert solvent such as benzene, toluene, xylene or chloroform at room temperature to reflux temperature, according to the method of S. O. Lawesson et al., Nouv. J. Chim., 4, 47 (1980).

J=J-3: such are prepared by reacting 3,4,5,6-tetrahydrophthalic anhydride with an appropriate aniline in an inert solvent such as tetrahydrofuran or toluene to give an intermediate acid-amide. The resulting intermediate is dehydrated with DCC (1,3-dicyclohexylcarbodiimide) or like dehydrating/condensation agent Reference: U.S. Pat. No. 4,472,190.

J=J-4, Z=nitrogen, X=O, Y=O or S: 1-(ethoxycarbonyl)piperidazine is treated with an iso(thio)cyanate prepared from an appropriate aniline by conventional methods, and treating the resulting intermediate product with sodium hydride. Alternatively, an appropriate N-(alkoxycarbonyl)hydrazine is treated with an appropriate iso(thio)cyanate, and the resulting intermediate is cyclized with a base to provide a urazole. Alkylation of the disodium salt of the urazole with 1,4-dibromobutane or 1,5-dibromopentane yields the desired product. Reference: European Pat. No. 104484; German Offenlegungschrift No. 3,504,051. J-4 compounds wherein Z=carbon, X=O or S, Y=O: ethyl pipecolinate is treated with the iso(thio)cyanate prepared from the appropriate aniline, in an inert solvent, such as THF, and the resulting (thio)urea intermediate is treated with ethanolic hydrogen chloride at reflux. Reference: U.S. Pat. No. 4,560,752. Thionation as described for J=J-1, provides those compounds wherein both X and Y=S.

J=J-5: these are prepared by methods analogous for those described for J=J-4, Z=carbon except that the (thio)urea intermediate is treated with either aqueous hydrochloric acid or sodium methoxide in methanol. Reference: European Pat. No. 70,389.

J=J-6: an appropriate aniline is diazotized and coupled with pipecolinic acid in the presence of triethylamine. Reference: U.S. Pat. Nos. 4,599,104; 4,002,636; 3,939,174.

J=J-7: an appropriate aniline is diazotized, and the product is reduced with stannous chloride to give a phenylhydrazine. The phenylhydrazine or its corresponding hydrochloride salt are condensed with a 2-(alkoxycarbonyl)cycloalkanone in an inert solvent such as toluene or ethanol, optionally in the presence of a basic catalyst such as triethylamine or sodium acetate, to afford an intermediate 4,5-fused-2,3-dihydropyrazol-3-one derivative. The intermediate is halogenated with phosphorous oxychloride or phosphorous oxybromide, optionally in the presence of a dehydrohalogenating agent such as N,N-diethylaniline at about 130°-160° C. to provide J-7 where R₉ is bromine or chlorine. Preparation of such compounds, and those wherein R₉ is other than halogen, is described in U.S. Pat. No. 4,059,434; U.S. Pat. No. 4,124,373, and European Pat. No. 138,527.

J=J-8: an appropriate aniline is converted to a phenylhydrazine, which is treated with 6-(hydroxyimino)-1-morpholinocyclohexene, and the resulting product is oxidized with cupric sulfate in pyridine. Reference: European Pat. No. 142,769.

J=J-9: an appropriate aniline is converted to a phenylhydrazine, which is treated with an acyl halide to form the acylhydrazide, which is treated with trichloromethyl chloroformate or phosgene, optionally in the presence of triethylamine. Reference: U.S. Pat. No. 3,385,862.

J=J-10: an appropriate aniline is converted to a phenylhydrazine hydrochloride salt, which is condensed with a cyclic iminoether derivative in an inert solvent such as tetrahydrofuran at about 25° C. to 67° C. to produce an amidrazone hydrochloride salt. The amidrazone is treated with thiophosgene, optionally in the presence of a base such as triethylamine, in an inert solvent such as dioxane at 80° C. to 105° C. to afford J-10 where X is sulfur. Alternatively, the amidrazone is treated with phosgene or trichloromethyl chloroformate, optionally in the presence of triethylamine, in an inert solvent such as dioxane at 80° C. to 105° C. to afford J-10 where X is oxygen. Reference: U.S. Pat. No. 4,213,773.

J=J-11: an iso(thio)cyanate prepared from the appropriate aniline is treated with trimethylsilyl azide (R₁₀ is hydrogen), which may be alkylated by conventional means. Reference: WIPO patent WO 85/01939 and EP-A 161, 304.

J=J-12: an appropriate aniline is diazotized and treated with malonyldiurethane. The resulting product is cyclized by treatment first with ethanolic potassium hydroxide in THF, then with aqueous hydrochloric acid to give a triazinedionecarboxylic acid, which is decarboxylated in the presence of mercaptoacetic acid and xylene to give J-12 wherein R₁₀ is hydrogen. Alternatively, an appropriately substituted aniline is diazotized and coupled with N-cyanoacetylurethane to afford an ethyl N-((aryl)cyanoacetyl) carbamate, which is cyclized in refluxing xylene in the presence of molecular sieves to remove ethanol. The resulting triazinedionecarbonitrile intermediate is then hdrolyzed with refluxing hydrochloric acid, and the resulting carboxylic acid is decarboxylated at 200°-250° C., optionally in the presence of an inert solvent such as Dowtherm®, to produce J-12 where R₁₀ is hydrogen. Alkylation of J-12 where R₁₀ is hydrogen is effected by reacting with sodium hydride and an alkyl halide in a suitable inert solvent such as DMF at about 0° C. to room temperature to afford J-12 wherein R₁₀ is one of the defined moieties. Reference: PCT application WO 86/00072. The patent also describes other suitable methods.

J=J-13; these are prepared by treating tetrahydrohomophthalic acid (2-carboxycyclohexene-1-acetic acid: (R. Grewe and A. Mondon, Chemische Berichte, volume 81, pages 279-286 (1948)), at page 283) with an appropriate aniline in refluxing acetic acid solvent.

J=J-14: an isocyanate prepared from an appropriate aniline is treated with sarcosine methyl ester hydrochloride in the presence of triethylamine, followed by treatment of the resulting urea with aqueous ethanolic hydrogen chloride. Reference: U.S. Pat. No. 4,560,752.

J=J-15: an appropriate aniline is converted to a phenylhydrazine, which is condensed with an α-ketoacid to form a hydrazone. The hydrazone is treated with diphenylphosphoryl azide in the presence of triethylamine in refluxing toluene to give a J-15 compound wherein R₈ is one of the defined moieties other than chlorine and R₁₀ is hydrogen. Alkylation of J-15 where R₁₀ is hydrogen is effected by reaction with sodium hydride and an alkyl halide in an inert solvent such as THF at about 0° C. to room temperature to produce J-15 wherein R₁₀ is one of the defined moieties. References: U.S. Pat. Nos. 4,213,773; 4,315,767; WIPO patent WO 85/01637.

An appropriate aniline or isocyanate reagent can be prepared from a compound of Formula I, wherein J is other than one of those defined herein, prepared by methods described herein. In such a case, the moiety J might appropriately by one of benzhydrylamino, benzoylamino or acetylamino, benzylamino, allylamino and trichloroacetylamino. As is shown in the examples, the aniline or isocyanate can be prepared from the J compound by conventional means.

It is to be understood that the following classes of compounds are novel and constitute aspects of this invention:

(1) Compounds of Formula I, including those wherein J is one of J-1 through J-15, those wherein J is one of the moieties described in the paragraph immediately above, and those wherein J is amino (--NH₂) or isocyanato (--NCO);

(2) Compounds of Formula II;

(3) Compounds of Formula III;

(4) Compounds of Formula IV;

(5) Compounds of Formula V;

(6) Compounds of Formula VI;

(7) Compounds of Formula IIA;

(8) Compounds of Formula XII;

(9) Compounds of Formula XIII;

(10) Compounds of Formula XIV;

(11) Compounds of Formula XV;

(12) Compounds of Formula XVI;

(13) Compounds of Formula XVII;

(14) Compounds of Formula XVIII;

(15) Compounds of Formula XIX;

(16) Compounds of Formula XX;

(17) Compounds of Formula XXI.

The preparation, isolation and testing of typical individual species of the compounds of Formulae I are described in the examples, following. The genus of compounds is further illustrated and exemplified by the following further individual species in Tables 1 to 21, all of which are specifically contemplated in this invention. In the interest of brevity, and clarity, and to avoid repetition of long chemical names, these species will be identified in terms of Formula I and the other symbols used therein.

The following examples further exemplify the invention. In each case, the identity of each product, and each of any intermediate involved, was confirmed by appropriate chemical and spectral analyses.

EXAMPLE 1 N-(2,3-dihydro-2-methyl-6-benzofuranyl)-3,4,5,6-tetrahydrophthalimide

A mixture of 25.0 g of 3,4,5,6-tetrahydrophthalic anhydride (THPA), 17.9 g of 3-aminophenol and 350 mL of glacial acetic acid was refluxed for 1 hour, then cooled and poured slowly into 1400 mL of ice-water. The resulting mixture was filtered, The collected solids were washed with cold water and dried (oven, reduced pressure) to give N-(3-hydroxyphenyl)-3,4,5,6-tetrahydrophthalimide (1A), as yellow crystals, mp.: 196°-197.5° C.

3.0 g of powdered potassium carbonate, then 2.6 g of allyl bromide were added to a stirred suspension of 5.0 g of 1A in 25 mL of acetone. The mixture was refluxed for 1 hour, then stirred overnight at room temperature. The solvent was evaporated, water was added to the residue and the pH of the mixture was adjusted to 11 by addition of 10% aqueous sodium hydroxide. The resulting mixture was extracted with ethyl acetate, the extract was washed with brine and dried (Na₂ SO₄), the solvent was evaporated and the residue was flash chromatographed on silica gel with a 1:9 v:v mixture of ethyl acetate and hexane as eluent to give N-(3-allyloxyphenyl)-3,4,5,6-tetrahydrophthalimide (1B), as yellow crystals, m.p.: 88°-90° C.

1 g of 1B was heated on an oil bath at 200°-210° C. for 5 hours and the product was flash chromatographed on silica gel with a 1:4 v:v mixture of ethyl acetate and hexane as eluent. Two products were isolated, N-(4-allyl-3-hydroxyphenyl)-3,4,5,6-tetrahydrophthalimide (1C), as yellow crystals, m.p.: 147°-148° C. and N-(2-allyl-3-hydroxyphenyl)-3,4,5,6-tetrahydrophthalimide (1D), as a white solid, m.p.: 72°-75° C.

A mixture of 0.20 g of 1C, 100 mg of p-toluenesulfonic acid (PTSA), and 10 mL of xylene was refluxed for 24 hours, then cooled and poured into a saturated aqueous solution of sodium bicarbonate. The resulting mixture was extracted with ethyl acetate, and the extract was washed with succession with sodium bicarbonate solution, water and brine, dried (Na₂ SO₄) and filtered. The solvent was evaporated and the residue was chromatographed on a Chromatotron™ plate, starting with a 3:17 v:v mixture of ethyl acetate and hexane as eluent and gradually increasing the ethyl acetate content in the eluent, to give the title compound, as yellow crystals, m.p.: 114°-118° C.

EXAMPLE 2 N-(2,3-dihydro-2-methyl-4-benzofuranyl)-3,4,5,6-tetrahydrophthalimide

Example 2 was prepared, as a yellow oil, by treating 0.48 g of 1D with PTSA in xylene according to the procedures described in Example 1.

EXAMPLE 3 N-(7-chloro-2,3-dihydro-2-methyl-4-benzofuranyl)-3,4,5,6-tetrahydrophthalimide

A mixture of 7.4 g of 2-chloro-5-nitrophenol, 5.4 g of allyl bromide, 5.9 g of anhydrous potassium carbonate and 50 mL of dry N,N-dimethylformamide (DMF) was stirred at room temperature over a weekend. Then the mixture was poured into water, and the resulting mixture was extracted twice with ethyl acetate and twice with ether. The combined extracts were washed with water, then with brine, dried (Na₂ SO₄), filtered and stripped of the solvents. The residue was recrystallized from hexane to give 1-(allyloxy)-2-chloro-5-nitrobenzene (3A), as orange needles, m.p.: 58°-59.5° C.

A suspension of 1.0 g of 3A and 5.3 g of stannous chloride dihydrate in 10 mL of absolute ethanol was heated for 1 hour. The resulting mixture was poured into 100 g of ice, then sufficient 10% aqueous sodium hydroxide solution was added, with stirring, to bring the pH of the mixture to 10. The mixture was extracted with ethyl acetate, then with ether. The combined extracts were washed with water, then brine, then dried (Na₂ SO₄) and stripped of the solvents, to give 3-(allyloxy)-4-chloroaniline (3B), as a brown oil.

A mixture of 4.4 g of THPA, 5.3 g of 3B and 60 mL of glacial acetic acid was refluxed for 1 hour, then poured into 300 mL of ice water. The resulting mixture was allowed to stand for 10 minutes, then filtered. The collected solid was washed with cold water, dried under reduced pressure and recrystallized from ethyl acetate/hexane, to give N-(3-(allyloxy)-4-chlorophenyl)-3,4,5,6-tetrahydrophthalimide (3C), as yellow crystals, m.p.: 118.5°-120° C.

7.2 g of 3C was heated at 210° C. for 1.5 hours, then the product was cooled and flash chromatographed on silica gel, with a 1:5 v:v mixture of ethyl acetate and hexane as eluent, to yield a viscous yellow oil that solidified on standing to give N-(2-allyl-4-chloro-3-hydroxyphenyl)-3,4,5,6-tetrahydrophthalimide (3D), m.p.: 80°-82.5° C.

The title compound was prepared, as yellow crystals, m.p.: 134°-137° C., from 3D by the procedures described in Example 1.

EXAMPLE 4 N-(7-chloro-2,3-dihydro-2-(hydroxymethyl)-4-benzofuranyl)-3,4,5,6-tetrahydrophthalimide

A solution of 1.50 g of 80% m-chloroperbenzoic acid (MCPBA) in 20 mL of 1,2-dichloroethane was added dropwise to a solution of 2.0 g of 3D in 25 mL of 1,2-dichloroethane at room temperature. The resulting mixture was heated at 70° C. for four hours, cooled and extracted with saturated aqueous sodium sulfite solution, until no reaction to starch/iodide paper occurred. The organic phase was separated, washed with saturated aqueous sodium bicarbonate solution, water, brine, dried (Na₂ SO₄) and stripped of solvent. The residue was flash chromatographed over silica gel, with a 2:3 v:v mixture of ethyl acetate and hexane as eluent, to obtain the title compound, as yellow crystals, m.p.: 193°-195° C.

EXAMPLE 5 N-(2,3-dihydro-2,7-dimethyl-4-benzofuranyl)-3,4,5,6-tetrahydrophthalimide

N-(2-allyl-3-hydroxy-4-methylphenyl)-3,4,5,6-tetrahydrophthalimide (5A) was prepared, as yellow crystals, m.p.: 141°-143° C., from 2-methyl-5-nitrophenol and allyl bromide by the procedures described in Example 3 for preparing 3D from 2-chloro-5-nitrophenol and allyl bromide.

The title compound was prepared, as yellow crystals, m.p.: 158°-160° C., from 5A, according to the procedure described in Example 1.

EXAMPLE 6 N-(2,3-dihydro-2-(hydroxymethyl)-7-methyl-4-benzofuranyl)-3,4,5,6-tetrahydrophthalimide

The title compound was prepared, as yellow crystals, m.p.: 177°-179° C., from 5A, by the procedures described in Example 4.

EXAMPLE 7 N-(2-((allyloxyimino)methyl)-7-chloro-2,3-dihydro-4-benzofuranyl)-3,4,5,6-tetrahydrophthalimide

A solution of 40 microliters of oxalyl chloride in 4 mL of methylene chloride was stirred under argon at -60° C. 65 microliters of dimethyl sulfoxide was added, and the mixture was stirred for 10 minutes. A solution of 0.1 g of Example 4 in 4 mL of methylene chloride was added and the mixture was stirred for 30 minutes. 0.28 mL of triethylamine was added and the mixture was allowed to warm to room temperature. 4 mL of dry pyridine and 40 mg of allyloxyamine hydrochloride were added and the mixture was stirred at room temperature for 1.5 hours. The solvents were removed by distillation with toluene; the residue was dissolved in ethyl acetate, the solution was filtered and the filtrate was chromatographed on a Chromatotron™ plate; by using initially a 1:9 v:v mixture of ethyl acetate and hexane as eluent and gradually increasing the ethyl acetate content; the title compound was obtained, as a yellow oil.

EXAMPLE 8 N-(2-(acetoxymethyl)-7-chloro- 2,3-dihydro-4-benzofuranyl)-3,4,5,6-tetrahydrophthalimide

The title compound, the acetic acid ester of Example 4, was obtained as a yellow glass, by treating Example 4 with acetic anhydride in the presence of 4-(dimethylamino)pyridine (DMAP) and pyridine.

EXAMPLE 9 N-(2-carboxy-7-chloro-2,3-dihydro-4-benzofuranyl)-3,4,5,6-tetrahydrophthalimide

The alcohol, from Example 4, was converted to the title acid, which was obtained as a beige solid, m.p.: 215°-217° C., by treating the alcohol with Jones' Reagent.

EXAMPLE 10 N-(2-(bromomethyl)-7-chloro-2,3-dihydro-4-benzofuranyl)-3,4,5,6-tetrahydrophthalimide

1.67 g of Example 4 was dissolved in a minimum amount of methylene chloride. 2.07 g of carbon tetrabromide was added, then the solution was stirred under nitrogen at 5° C. while 2.0 g of triphenylphosphine was added in portions over 10 minutes. The mixture was stirred for 10 minutes in an ice bath, then for 4 hours at room temperature. The solvent was evaporated; the residue was triturated with a 9:1 v:v mixture of ether and hexane. The supernatant liquid was decanted and stripped of solvent and the residue was flash chromatographed on silica gel, by using a 1:4 v:v mixture of ethyl acetate and hexane as eluent, to give the title compound, as white crystals, m.p. 134°-136° C.

EXAMPLE 11 N-(2-(tert-butoxycarbonyl)-2,3-dihydro-7-chloro-4-benzofuranyl)-3,4,5,6-tetrahydrophthalimide

0.33 g of Example 4 was dissolved in a minimum amount of methylene chloride. 1.5 g of tert-butyl alcohol, 1.0 mL of acetic anhydride and 0.75 g of pyridinium dichromate were added, and the mixture was stirred for 1 hour at room temperature. The mixture was flushed through silica gel, the column was rinsed with methylene chloride, the solvent was evaporated and the residue was chromatographed on silica gel, by using a 1:4 mixture of ethyl acetate and hexane as eluent, to give the title compound, as a yellow glass.

EXAMPLE 12

The acetic acid ester of Example 6 was obtained as a yellow solid, m.p.: 130°-132° C., by treating Example 6 with acetic anhydride in the presence of DMAP and pyridine.

EXAMPLES 13 AND 14

The methyl ester--i.e., Example 13, obtained as a yellow solid, m.p.: 121°-123° C.--and the ethyl ester--i.e., Example 14, obtained as a yellow solid, m.p.: 71°-76° C.--were prepared by treating Example 9 with methanol and ethanol, respectively, in the presence of PTSA.

EXAMPLES 15 AND 16

The ammonium salt--i.e., Example 15, obtained as a white powder, m.p.: 197°-198° C. (with decomposition)--and the isopropylamine salt--i.e., Example 16, obtained as a tan solid, m.p.: 211°-213° C. (with decomposition)--of Example 9 were prepared by treating Example 9 with ammonia gas and isopropylamine, respectively.

EXAMPLE 17

The sodium salt of Example 9 was prepared, as a yellow powder, m.p.: 280°-284° C. (with decomposition) by treating Example 9 in ethanol with a water solution of sodium bicarbonate.

EXAMPLE 18

The alcohol of Example 6 was converted to the acid, Example 19, obtained as a tan solid, m.p.: 229°-231° C. (with decomposition) by treating the alcohol with Jones' reagent.

EXAMPLE 19 N-(7-Chloro-2,3-dihydro-5-fluoro-2-methyl-4-benzofuranyl)-3,4,5,6-tetrahydrophthalimide

(3-(allyloxy)-4-chloro-6-fluoroaniline (19A) was prepared, as a brown oil, from 2-chloro-4-fluorophenol and allyl bromide by procedures described in U.S. Pat. No. 4,452,981.

A mixture of 9.0 g of 19A, 6.8 g of THPA and 100 mL of glacial acetic acid was heated at reflux temperature for 4 hours. The resulting mixture was cooled to room temperature, poured into 450 mL of water and extracted with ether. The extract phase was washed with water, dried (Na₂ SO₄), and filtered, and the solvent was evaporated from the filtrate. The residue was flash-chromatographed on silica gel, with a 15:85 v:v mixture of ethyl acetate and hexane as eluent, to give N-(3-allyloxy)-4-chloro-6-fluorophenyl)-3,4,5,6-tetrahydrophthalimide (19B), as an orange oil.

9.8 g of 19B was heated in an oil bath at 200° C. for one hour. The resulting crude product was cooled to room temperature and flash chromatographed on silica gel, by using a 5:95 v:v mixture of acetone and toluene as solvent, to give N-(2-allyl-4-chloro-6-fluoro-3-hydroxyphenyl)-3,4,5,6-tetrahydrophthalimide (19C), as a tan solid, m.p.: 109°-111° C.

A mixture of 80 mL of xylene and 0.5 g of PTSA monohydrate was dehydrated by azeotroping for 30 minutes. The resulting solution was cooled to room temperature, 1.70 g of 19C was added and the resulting mixture was heated at reflux for 18 hours, then held at room temperature overnight. The mixture was washed with a saturated aqueous solution of sodium bicarbonate, then with water, then with brine, dried (Na₂ SO₄), filtered and stripped of solvent. The residue was flash-chromatographed on silica gel, using a 1:4 v:v mixture of ethyl acetate and hexane as eluent, to give the title compound, as off-white crystals, m.p.: 169°-171° C.

EXAMPLE 20 N-(7-Chloro-2,3-dihydro-5-fluoro-2-(hydroxymethyl)-4-benzofuranyl)-3,4,5,6-tetrahydrophthalimide

A solution of 0.67 g of 19C and 475 mg of 80% MCPBA in 15 mL of 1,2-dichloroethane was heated on an oil bath at 70° C. for 2.5 hours. A few milligrams of PTSA was added, the mixture was cooled to room temperature, washed with a saturated aqueous solution of sodium sulfite, followed by a saturated aqueous solution of sodium bicarbonate, dried (Na₂ SO₄), filtered and stripped of solvent. The residue was flash chromatographed on silica gel with a 40:60 v:v mixture of ethyl acetate and hexane as eluent, to give the title compound, as white crystals, m.p.: 193°-195° C.

EXAMPLE 21 N-(2-(acetoxymethyl)-7-chloro-2,3-dihydro-5-fluoro-4-benzofuranyl)-3,4,5,6-tetrahydrophthalimide

The title compound, the acetic acid ester of Example 20, was obtained, as off-white crystals, m.p.: 129°-131° C., by treating Example 20 with acetic anhydride in the presence of DMAP and pyridine.

EXAMPLE 22 N-(2-carboxy-7-chloro-2,3-dihydro-5-fluoro-4-benzofuranyl)-3,4,5,6-tetrahydrophthalimide

The title compound was obtained, as a white powder, m.p.: 209°-211° C. (with decomposition) by treating Example 20 with Jones' Reagent.

EXAMPLE 23 N-(7-chloro-2,3-dihydro-5-fluoro-2-(methoxycarbonyl)-4-benzofuranyl)-3,4,5,6-tetrahydrophthalimide

The title compound was prepared, as a yellow semi-solid, by treating Example 22 with methanol in the presence of PTSA.

EXAMPLE 24 N-(7-chloro-2,3-dihydro-2-((1-ethoxycarbonyl)ethoxycarbonyl)-5-fluoro-4-benzofuranyl)-3,4,5,6-tetrahydrophthalimide

A mixture of 0.300 g of Example 22, 120 microliters of ethyl 2-bromopropionate, 0.136 g of potassium carbonate, 0.136 g of potassium iodide and 8 mL of acetonitrile was heated at reflux for 3 hours. The resulting mixture was partitioned between ether and water; the ether phase was separated, washed with water, then brine, dried (MgSO₄), filtered and stripped of solvent. The residue was flash chromatographed on silica gel, by using a 1:3 v:v mixture of ethyl acetate and hexane as eluent, to give the title compound, as a yellow semi-solid.

EXAMPLE 25 N-(7-chloro-2,3-dihydro-2-(hydroxymethyl)-4-benzofuranyl)phthalimide

The title compound was prepared, as a white solid, m.p.: 181°-183° C., from 3B and phthalic anhydride in three steps, according to the procedures described for preparing Example 4 from 3D.

EXAMPLE 26

N-(2-carboxy-7-chloro-2,3-dihydro-4-benzofuranyl)phthalimide was prepared as beige crystals, m.p.: 236°-239° C. (with decomposition) by treating Example 25 with Jones' Reagent.

EXAMPLES 27-30

By procedures described in the foregoing examples, the following compounds of Formula I were prepared

Example 27, the ethyl ester of Example 26, as a yellow solid, m.p.: 134°-136° C.;

Example 28, the methyl ester of Example 26, as a yellow solid, m.p.: 136°-138° C.;

Example 29, the sodium salt of Example 26, as a yellow solid, m.p.: not determined (decomposition above 300° C.);

Example 30, the ammonium salt of Example 26, as a yellow powder, m.p.: 220°-223° C. (with decomposition).

EXAMPLE 31 N-(7-chloro-2,3-dihydro-2,3-dihydro-2-methyl-4-benzofuranyl)phthalimide

The title compound was prepared, as a beige solid, m.p.: 197°-198° C., from 3B and phthalic anhydride, by the procedures described for preparing Example 3 from 3B.

EXAMPLE 32 2-(7-Chloro-2,3-dihydro-2-methyl-4-benzofuranyl-4-methyl-3,5-dioxo-1,2,4-triazine-3,5(2H,4H)-dione

15 g of hydrazine was added to a mixture of 30 g of Example 31 and 120 mL of dimethyl sulfoxide under nitrogen at room temperature. The mixture was stirred for 16 hours, then was added to 600 mL of water. The mixture was extracted with ether, the extract was washed with water, then with brine, dried and stripped of solvent to give 4-amino-7-chloro-2,3-dihydro-2-methylbenzofuran (32A), as a solid, m.p.: 70° C.

A mixture of 9.18 g of 32A, 10 mL of 12N hydrochloric acid and 10 mL of water was heated on a steam bath for 1 hour, then 10 mL of water was added and the mixture was stirred at room temperature overnight. Then 30 mL of water was added, the mixture was cooled to 0° C. and stirred while a solution of 3.45 g of sodium nitrite in 10 mL of water was added dropwise over 15 minutes, then was stirred for 1 hour at 0° C. The resulting mixture was added slowly to a stirred mixture of 7.8 g of N-cyanoacetylurethane, 35 mL of pyridine and 900 mL of water, at 0° C. The resulting mixture was stirred at 0° C. for 1.5 hours, and filtered. The collected solid phase was washed with water, dried under reduced pressure and recrystallized from acetone/petroleum ether to give ethyl N-((7-chloro-2,3-dihydro-2-methyl- 4-benzofuranylhydrazono)cyanoacetyl)carbamate (32B), as a solid, m.p.: 175°-177° C. (with decomposition).

A mixture of 12.5 g of 32B and 600 mL of xylene was stirred at reflux temperature overnight under a Soxhlet extractor filled with 4A molecular sieves to collect the alcohol that was formed. The mixture was cooled to room temperature and filtered; the solid product was dried under reduced pressure to give 2-(7-chloro-2,3-dihydro-2-methyl-4-benzofuranyl)-2,3,4,5-tetrahydro-3,5-dioxo-1,2,4-triazine-6-carbonitrile (32C) as a tan solid, m.p.: 244°-245° C.

A mixture of 9.0 g of 32C, 150 mL of p-dioxane and 100 mL of 6N hydrochloric acid was stirred at reflux temperature overnight. Then 20 mL of 12N hydrochloric acid was added and the mixture was stirred at reflux temperature for 2 hours, and stripped of solvent. The residue was dissolved in ethyl acetate, the solution was washed with water, then brine, dried (MgSO₄) and stripped of solvent. The residue was recrystallized from ethyl acetate/petroleum ether to give 2-(7-chloro-2,3-dihydro-2-methyl-4-benzofuranyl)-2,3,4,5-tetrahydro-3,5-dioxo-1,2,4-triazine-6-carboxylic acid (32D), as an amber solid, m.p.: 235°-236° C. (with decomposition).

A mixture of 8.0 g of 32D and 80 mL of Dowtherm® was heated at 200°-250° C. for 2 hours, cooled to room temperature, diluted with petroleum ether and filtered. The collected solid phase was dried under reduced pressure, and recrystallized from ethyl acetate/petroleum ether to give 2-(7-chloro-2,3-dihydro-2-methyl-4-benzofuranyl)-1,2,4-triazine-3,5(2H,4H)-dione, (32E) as a tan solid, m.p.: 184°-186° C.

2.8 g of 32E was added over 15 minutes to a stirred mixture of 0.5 g of hexane-washed sodium hydride, 1.6 g of methyl iodide and 30 mL of dry DMF, under nitrogen at 0° C. When gas evolution ended (30 minutes) the mixture was stirred at room temperature for 1.5 hours, poured into ice-water and the resulting mixture was filtered. The collected solid was dissolved in ethyl acetate; the resulting solution was washed with water, then brine, dried (MgSO₄) and stripped of solvent. The residue was recrystallized from ethyl acetate/hexane to give the title compound, as a tan solid, m.p.: 131°-132° C.

EXAMPLES 33 2-(7-chloro-2,3-dihydro-2-methyl-4-benzofuranyl)-4-(difluoromethyl)-5-methyl-2H-1,2,4-triazol-3(4H)-one

5.5 g of 32A was diazotized by the procedure described in Example 32. The diazotization mixture was cooled to -25° C. and a solution of 19.7 g of tin(II) chloride dihydrate in 25 mL of 12N hydrochloric acid was added dropwise over 20 minutes to the stirred mixture, which was stirred thereafter at -25° C. for 4 hours. Then a solution of 2.82 g of redistilled pyruvic acid in 20 mL of water was added dropwise to the stirred mixture at -25° C., then while being stirred was allowed to warm slowly to room temperature and stirred over a weekend. Then the mixture was filtered, and the solid material was washed with water and dissolved in a saturated aqueous solution of sodium bicarbonate. The solution was extracted with ethyl acetate, and the aqueous phase was acidified with 12N hydrochloric acid and extracted with ethyl acetate. The latter extract was washed with water, then with brine, dried (MgSO₄) and stripped of solvent. The residue was recrystallized from ethyl acetate/hexane to give 2-((7-chloro-2,3-dihydro-2-methyl-4-benzofuranyl)hydrazono)propanoic acid (33A), a mixture of isomers, m.p.: 155°-157° C.

5.1 g of triethylamine was added to a stirred mixture of 5.0 g of 33A and 100 mL of toluene, then 1.9 g of diphenylphosphoryl azide was added and over two hours the mixture was heated to and held at reflux temperature. The resulting mixture was poured into 110 mL of 10% w:v aqueous ice-cold potassium hydroxide solution. Two liquid phases resulted and were separated. The aqueous phase was acidified with 12N hydrochloric acid, and extracted with ethyl acetate. The extract was washed with water, then with brine, dried (MgSO₄) and stripped of solvent. The residue was recrystallized from ethyl acetate/hexane to give 2-(7-chloro-2,3-dihydro-2-methyl-4-benzofuranyl)-5-methyl-2H-1,2,4-triazol-3(4H)-one (33B), as a colorless solid, m.p.: 208°-209° C.

A mixture of 0.6 g of hexane-washed sodium hydride and 30 mL of THF was saturated with Freon 22 (chlorodifluoromethane) at 0° C., then a mixture of 1.33 g of 33B and 10 mL of THF was added and the mixture was stirred at room temperature for 6 hours, Freon 22 being bubbled into the mixture throughout that period. The mixture was stirred at room temperature for a week, 15 mL of water was added dropwise, and the solvent was stripped. The residue was dissolved in ethyl acetate, the solution was washed with water, then with brine, dried (MgSO₄) and stripped of solvent. The residue was chromatographed on silica gel, with a 1:3 v:v mixture of hexane and methylene chloride as eluent to give the title compound, as a colorless solid, m.p.: 122.5°-123.5° C., and the isomeric 2-(7-chloro-2,3-dihydro-2-methyl-4-benzofuranyl)-1-(difluoromethyl)-5-methyl-1H-1,2,4-triazol-3(2H)-one, as a cream-colored solid, m.p.: 78°-79° C.

EXAMPLE 34 2-(7-chloro-2,3-dihydro-2-methyl-4-benzofuranyl)hexahydro-1H-imidazo[3,4-a]pyridine-1,3(2H)-dione

6.07 g of triethylamine was added to a mixture of 9.18 g of 32A, 11.87 g of trichloromethyl chloroformate and 250 mL of dioxane, and the mixture was refluxed for 6 hours. The mixture was cooled, filtered, and the filtrate was stripped of solvent, to give 7-chloro-2,3-dihydro-4-isocyanato-2-methylbenzofuran (34A), as a brown liquid.

A solution of 2.36 g of ethyl pipecolinate in 20 mL of dry THF was added, at room temperature under nitrogen, to a mixture of 2.10 g of 34A and 60 mL of dry THF, the rate of addition being such as to maintain the temperature of the mixture at 25°-32° C., then the mixture was stirred overnight at room temperature, diluted with 250 mL of hexane and filtered. The collected solid phase was identified as ethyl 1-(((7-chloro-2,3-dihydro-2-methyl-4-benzofuranyl)amino)carbonyl)-2-piperidinecarboxylate (34B), m.p.: 169°-171° C.

A mixture of 2.0 g of 34B, 25 mL of ethanol and 25 mL of 2N hydrochloric acid was stirred and refluxed for 2 hours. Then the solvent was evaporated, the residue was mixed with 50 mL of water, and the resulting mixture was extracted with methylene chloride The extract was dried (MgSO₄) and the solvent was evaporated. The residue was purified by filtration through a short pad of silica gel, with a 1:1 v:v mixture ethyl acetate and hexane as eluent, to give the title compound, as a solid, m.p.: 145°-148° C.

EXAMPLE 35 3-(7-Chloro-2,3-dihydro-2-methyl-4-benzofuranyl)-1-methylimidazolidine-2,4-dione

2.30 g of sarcosine ethyl ester hydrochloride was added over 5 minutes to a mixture of 2.10 g of 34A, 1.52 g of triethylamine and 60 mL of methylene chloride, under nitrogen at 25°-30° C. The mixture was stirred at room temperature for 24 hours, then diluted with 100 mL of methylene chloride, washed with water, then brine, dried (MgSO₄) and stripped of solvent. The residue was dissolved in 70 mL of a 1:1 v:v mixture of ethanol and 2N hydrochloric acid. The solution was refluxed for 4 hours, the resulting mixture was stirred at room temperature overnight, stripped of volatiles, diluted with water and extracted with methylene chloride. The extract was dried (MgSO₄) and stripped of solvent. The residue was purified by flash chromatography over silica gel with a 1:2 v:v mixture of hexane and ethyl acetate as eluent to give the title compound, as a glass/sticky solid.

EXAMPLE 36 N-(7-Chloro-5-fluoro-2,3-dihydro-2-methyl- 4-benzofuranyl)phthalimide

The title compound was prepared, as a colorless solid, m.p.: 158.5°-160° C. from 3-(allyloxy)-4-chloro-6-fluoroaniline (19A) and phthalic anhydride by the procedures described for preparing Example 19 from 19A.

EXAMPLE 37 N-(7-Chloro-5-fluoro-2,3-dihydro-2-methyl-4-benzofuranyl)-3,4,5,6-tetrahydrohomophthalimide

8.3 g of hydrazine hydrate was added to a slurry of 11.0 g of Example 36 and 60 mL of dimethyl sulfoxide under nitrogen at 25°-35° C. The mixture was stirred at room temperature for 16 hours, then added to 250 mL of water. The mixture was extracted with ether, the extract was washed with water, brine, dried (MgSO₄) and stripped of solvent to give 4-amino-7-chloro-4-fluoro-2,3-dihydro-2-methyl-benzofuran (37A) as a light brown oil.

A mixture of 0.61 g of 3,4,5,6-tetrahydrohomophthalic acid, 0.55 g of 37A and 10 mL of acetic acid was refluxed for 19 hours and cooled. The solvent was removed in vacuo, the residue was purified by flash chromatography on silica gel, eluting with a 1:1 v:v mixture of ether and hexane to give the title compound as a cream colored solid, m.p. 124.5°-126.5° C.

EXAMPLE 38 5-tert-Butyl-3-(5,7-dichloro-2,3-dihydro-2-methyl-4-benzofuranyl)-1,3,4-oxadiazol-2(3H)-one

4-amino-5,7-dichloro-2,3-dihydro-2-methylbenzofuran (38A) was prepared as an orange oil in four steps from 3-(allyloxy)-4,6-dichloroaniline and phthalic anhydride by the procedures described for preparing Example 19 from 19A, followed by hydrazinolysis of the phthalimide intermediate as described for the preparation of 37A.

2.19 g of 38A was suspended in 9 mL of concentrated H₂ SO₄ and 9 mL of water at -5° C. A solution of 0.69 g of sodium nitrite in 4 mL of H₂ O was added slowly and the resulting solution was stirred at 0° C. for one hour. This solution was added slowly to a mixture of 4.51 g of tin (II) chloride in 15 mL of concentrated hydrochloric acid which was precooled to -10° C., so as to maintain -10° C. to -5° C. The mixture was slowly warmed to room temperature and stirred for 16 hours. With cooling, 50% sodium hydroxide solution was added to adjust the pH to 11. The mixture was extracted with ether. The extract was washed with water, brine, dried (MgSO₄) and stripped of solvent to leave crude 5,7-dichloro-2,3-dihydro-4-hydrazino-2-methylbenzofuran (38B), as pale orange solid, m.p.: 59°-64° C.

To a solution of 0.73 g of 38B and 0.38 g of triethylamine in 10 mL of dry THF at 0° C. under nitrogen was added a solution of 0.38 g of trimethylacetyl chloride in 2 mL of dry THF. The mixture was stirred at room temperature overnight, filtered, and evaporated. The residue was purified by flash chromatography on silica gel, using a 1:2 v:v mixture of ethyl acetate and hexane to afford the intermediate trimethylacetylphenylhydrazide (38C) as a solid, m.p.: 116°-118.5° C.

To a solution of 0.51 g of 38C and 0.32 g of trichloromethyl chloroformate in 20 mL of dry dioxane was added 0.20 g of triethlamine. The resulting mixture was refluxed under nitrogen for 7 hours, cooled to room temperature, filtered and evaporated. The residue was purified by flash chromatography on silica gel, eluting with a 1:4 v:v mixture of ethyl acetate and hexane to afford the title compound as a yellow solid, m.p.: 112°-115° C.

IR (cm⁻¹): 1775, 1610.

NMR (CDCl₃, 200 MHz) δ1.38 (s, 9H) 1.55 (d, 3H, J=6 Hz) 2.93 (dd, 1H; J=16, 8 Hz) 3.43 (dd, 1H; J=16, 9 Hz) 5.12 (m, 1H) 7.30 (s, 1H).

EXAMPLE 39 3-Chloro-2-(7-chloro-4-fluoro-2,3-dihydro-2-methyl-4-benzofuranyl)-4,5,6,7-tetrahydro-2H-indazole

7-chloro-4-fluoro-2,3-dihydro-4-hydrazino-2-methylbenzofuran (39A) was prepared as a low melting semisolid from 37A by diazotization and reduction with tin (II) chloride by the procedures described for preparing 38B from 38A. Reaction of 39A with hydrogen chloride gas in ether provided the corresponding arylhydrazine hydrochloride (39B) as a light brown solid, m.p.: 169°-172° C.

A mixture of 0.51 g of 39B, 0.34 g of ethyl cyclohexanone 2-carboxylate and 0.16 g of anhydrous sodium acetate in 10 mL of ethanol was refluxed under nitrogen for three days, cooled to room temperature, and the solvent was removed in vacuo. The residue was slurried in ether, filtered, and the filtrate residue was triturated with ether to afford 2-(7-chloro-4-fluoro-2,3-dihydro-2-methyl-4-benzofuranyl)-1,2,4,5,6,7-hexahydro-3H-indazol-3-one (39C) as a colorless solid, m.p.: 240°-242° C.

0.25 g of 39C was mixed with 0.14 g of phosphorous oxychloride and 0.15 g of N,N-diethylaniline and heated under nitrogen at 135°-140° C. for three hours, cooled, and diluted with ethyl acetate. The organic phase was washed with water, 10% hydrochloric acid, saturated sodium bicarbonate solution, brine, dried (MgSO₄) and stripped of solvent. The residue was purified by flash chromatography on silica gel, using a 1:4 v:v mixture of ether and hexane as eluent to afford the title compound as a yellow glass.

NMR (CDCl₃, 200 Mhz) δ 1.53 (d, 3H, J=6 Hz) 1.83 (m, 4H) 2.50 (t, 2H, J=5 Hz) 2.70 (t, 2H, J=5 Hz) 2.90 (m, 1H) 3.35 (m, 1H) 5.10 (m, 1H) 7.05 (d, 1H, J=9 Hz).

EXAMPLE 40 3-(7-Chloro-2,3-dihydro-2-methyl-4-benzofuranylimino)-4,5,6,7-tetrahydro-1(3H)-isobenzofuranone

To a solution of 1.52 g of THPA in 10 mL of dry THF under nitrogen was added a solution of 1.84 g of 32A in 5 mL of dry THF. After 10 minutes, 50 mL of dry THF was added to facilitate stirring of the thick precipitate, and the mixture was stirred overnight. The solvent was removed in vacuo, the residue was slurried in ether/hexane, and the resultant solid was collected to give the intermediate acid-amide (40A) as a colorless solid.

2.95 g of 40A was slurried in 50 mL of benzene under nitrogen and treated with 1.81 g of 1,3-dicyclohexylcarbodiimide. After 18 hours at room temperature, the solution was diluted with 50 mL of hexane, filtered, and the solvent was removed to afford the title compound as a yellow solid, m.p.: 125°-127° C.

IR (cm⁻¹) 1780, 1680.

NMR (CDCl₃, 200 MHz) δ 1.55 (d, 3H, J=6 Hz) 1.85 (m, 4H) 2.42 (m, 2H) 2.55 (m, 2H) 2.85 (dd, 1H) 3.36 (dd, 1H) 5.06 (m, 1H) 6.75 (d, 1H, J=8 Hz) 7.12 (d, 1H, J=8 Hz).

EXAMPLE 41 2-(8-Chloro-6-fluoro-3,4-dihydro-2H-1-benzopyran-5-yl)-tetrahydro-1H-((1,2,4))triazolo(1,2-A)pyridazine-1,3(2H)-dione

A mixture of 20.2 g of 19A and 14.8 g of phthalic anhydride in 300 mL of toluene was treated with 1.01 g of triethylamine and heated to reflux for 16 hours with a Dean-stark trap to effect azeotropic removal of water. The toluene was removed in vacuo, The residue was dissolved in 800 mL of methylene chloride, and treated with 35 g charcoal. After filtration through celite and concentration of solvent in vacuo, the residue was recrystallized from ethanol to afford N-[3-(allyloxy)-4-chloro-6-fluorophenyl]-phthalimide (41A) as tan crystals, m.p.: 148°-150° C.

36.5 g of 41A was heated and stirred under a nitrogen atmosphere at 195° C. for 1 hour. After cooling, methylene chloride was added and the crude product was purified by flash chromatography on silica gel, eluting with methylene chloride. Removal of solvent afforded N-[2-allyl-4-chloro-6-fluoro-3-hydroxyphenyl]phthalimide (41B) as a nearly colorless solid, m.p.: 133.5°-135.5° C.

To a solution of 3.21 g of 41B dissolved in 10 mL dry THF under a nitrogen atmosphere was added dropwise over 10 minutes 9-BBN (38.7 mL of 0.5M in THF). After 10 minutes, the solution was heated to reflux for 1 hour, cooled to 0° C., 12 mL of ethanol was added, followed by 6.45 mL of 3M aqueous sodium acetate solution. With ice-bath cooling, 6.4 mL of 30% hydrogen peroxide was added dropwise so as to maintain a temperature of about 25° C. The mixture was then heated to 55° C. for 1 hour, cooled to 10° C. and acidified to a pH of 4 with 10% hydrochloric acid. The mixture was diluted with ethyl acetate, extracted with brine, saturated sodium sulfite solution, brine, dried over MgSO₄ and stripped of solvent. Addition of ethanol and refrigeration afforded N-[2-(3-hydroxy)propyl-4-chloro-6-fluoro-3 -hydroxyphenyl]phthalimide (41C) as a colorless solid, m.p.: 187°-188.5° C.

A mixture of 2.00 g of 41C and 0.54 g of PTSA·H₂ O in 50 mL of xylene was azeotropically refluxed with a Dean-stark trap for 18 hours. The solution was treated further with 0.54 g of PTSA·H₂ O and refluxed for 8 hours. The xylene was removed in vacuo and the residue was filtered through a pad of silica gel using methylene chloride as eluent to afford 8-chloro-6-fluoro-5-phthalimido chromane (41D) as a colorless solid, m.p.: 198°-200° C.

To a solution of 10.05 g of 41D in 60 mL of DMSO was added 7.58 g of hydrazine hydrate. The mixture was heated to 65°-75° C. for 3 hours, cooled, and poured into ice-water. The mixture was extracted with 3 portions of ether. The ether layer was extracted with water, brine, and dried over MgSO₄ to afford 5-amino-8-chloro-6-fluorochromane (41E) as a yellow oil which solidified on standing, m.p.: 47°-50° C.

8-chloro-6-fluoro-5-isocyanato-chromane (41F) was prepared, as a brown semisolid, from 41E, trichloromethyl chloroformate, and triethylamine by the procedures described for preparing 34A from 32A. A solution of 1.06 g of 41F dissolved in 10 mL of toluene was added under nitrogen to 0.50 g of methyl hydrazinocarboxylate in 15 mL of toluene. After stirring overnight at room temperature, 50 mL of hexane was added, and the product was collected by filtration to afford methyl 2-(((8-chloro-6-fluoro-3,4-dihydro-2H-1-benzopyranyl-5-amino)carbonyl))-hydrazine carboxylate (41G) as a colorless solid, m.p.: 218°-220° C.

A mixture of 1.49 g of 41G and 0.94 g of sodium hydroxide in 8 mL of water was refluxed for 3.5 hours, cooled, acidified to a pH of 3 with concentrated hydrochloric acid, and the resultant solid was collected by filtration to give 4-(8-chloro-6-fluoro-3,4-dihydro-2H-1-benzopyran-5-yl)-1,2,4-triazolidine-3,5-dione (41H) as a colorless solid, m.p.: 271°-273° C.

A solution of 0.55 g of 41H in 10 mL of dry DMF was added under nitrogen to a slurry of 0.096 g of sodium hydride in 20 mL of dry DMF. The mixture was heated to 55° C. for 1 hour, cooled to room temperature, treated with 0.46 g of 1,4-dibromobutane, and stirred at room temperature overnight. The mixture was poured into water, extracted with ether, the extracts were washed with water, brine, dried (MgSO₄) and stripped of solvent. The residue was purified by flash chromatography on silica gel using a 1:2 to 1:1 v:v gradient of ethyl acetate and hexane to afford the title compound as colorless crystals, m.p.: 185°-188° C.

IR (cm⁻¹): 1770, 1708.

NMR (CDCl₃, 300 MHz) δ 192 (m, 4H) 2.02 (pentet, 2H, J=6 Hz) 2.72 (t, 2H, J=6 Hz) 3.66 (m, 4H) 4.30 (t, 2H, J=5 Hz) 7.17 (d, 1H, J=8 Hz).

EXAMPLE 42 2-(5,7-Dichloro-2,3-dihydro-2-methyl-4-benzofuranyl)-5,6,7,8-tetrahydro-1,2,4-triazolo((4,3A))pyridine-3(2H)-one

(5,7-dichloro-2,3-dihydro-2-methyl-4-benzofuranyl)hydrazine hydrochloride (42A) was obtained as a pink solid, m.p.: 198°-200° C. by reaction of 38B with hydrogen chloride gas in ether.

A slurry of 0.61 g of 42A in 5 mL of dry THF was treated under nitrogen with 0.26 g of ethyl (3,4,5,6-tetrahydropyridyl)ether. The mixture was refluxed for 8 hours, cooled, an additional 0.03 g of ethyl (3,4,5,6-tetrahydropyridy)ether was added, and refluxing was continued for 4 hours. The solvent was removed in vacuo, the residue was slurried in refluxing ether, cooled, and collected by filtration to afford (5,7-dichloro-2,3-dihydro-2-methyl-4-benzofuranyl)-2-piperidinone hydrazone hydrochloride (42B) as a hygroscopic solid, m.p.: 79°-86° C.

0.44 g of triethylamine was added under nitrogen to a solution of 0.66 g of 42B and 0.45 g of trichloromethyl chloroformate in 30 mL of dry dioxane. The mixture was refluxed for 23 hours, cooled, filtered, and the filtrate residue was purified by flash chromatography on silica gel, using a 1:2 to 2:1 v:v gradient of ethyl acetate and hexane to afford the title compound as a light yellow solid, m.p.: 198°-202° C.

IR (cm⁻¹) 1700, 1575.

NMR (CDCl₃, 200 MHz) δ 1.52 (d, 3H, J=6 Hz) 1.98 (m, 4H) 2.77 (m, 2H) 2.93 (m, 1H) 3.37 (m, 1H) 3.70 (m, 2H) 5.09 (m, 1H) 7.29 (s, 1H).

EXAMPLE 43 7-Chloro-5-fluoro-4(2,3,4,5,6,7-hexahydro-1,3-dioxo-1H-isoindol-2-yl)-2,3-dihydro-N,N-dimethyl-2-benzofurancarboxamide

A mixture of 0.74 g of Example 22 in 10 mL of thionyl chloride was refluxed for 1 hour, cooled, stripped, and pumped under high vacuum to afford the corresponding acid chloride (43A) as a light yellow foam.

To a solution of 0.384 g of 43A in 5 mL of dry THF at 0° C. under nitrogen was added dropwise a solution of 0.17 g of dimethylamine hydrochloride and 0.24 g of triethylamine dissolved in 10 mL of dry THF. After one hour at 0° C., the mixture was stirred at room temperature for 2.5 hours, diluted with ethyl acetate, washed with 10% hydrochloric acid, water, brine, dried (MgSO₄) and stripped of solvent. The residue was purified by flash chromatography on silica gel, eluting with a 1:2 v:v mixture of ethyl acetate and hexane to afford the title compound as a pale yellow solid, m.p.: 190°-193° C.

IR (cm⁻¹): 2925, 1775, 1720, 1650.

NMR (CDCl₃), 200 MHz) δ 1.85 (m, 4H) 2.45 (m, 4H) 3.02 (s, 3H) 3.23 (s, 3H) 3.30 (dd, 1H, J=16, 10 Hz) 3.85 (dd, 1H, J=16, 7 Hz) 5.53 (dd, 1H, J=10, 7 Hz) 7.04 (d, 1H, J=9 Hz).

Using the above disclosures, one skilled in the art may readily prepare the following compounds.

                  TABLE 1                                                          ______________________________________                                          ##STR35##                                                                      ##STR36##                                                                     m      R      R.sub.1                                                                               R.sub.2                                                                              R.sub.3   m.p. (°C.)                         ______________________________________                                         1      H      Cl     H     CH.sub.2 OH                                                                              181-183                                   1      H      Cl     H     CO.sub.2 H                                                                               252-254 (dec)                             1      H      Cl     H     CO.sub.2 C.sub.2 H.sub.5                                                                 134-136                                   1      H      Cl     H     CH.sub.3  197-198                                   1      H      Cl     H     CO.sub.2 CH.sub.3                                                                        136-138                                   1      H      Cl     H     CO.sub.2 Na                                                                              >300 (dec)                                1      H      Cl     H     CO.sub.2 NH.sub.4                                                                        220-223 (dec)                             1      F      Cl     H     H                                                   1      F      Cl     H     CH.sub.3  158.5-160                                 1      F      Cl     H     CH.sub.2 OH                                                                              211-213                                   1      F      Cl     H     CO.sub.2 H                                                                               195.5-197.5                               1      F      Cl     H     CO.sub.2 C(CH.sub.3).sub.3                                                               63-67                                     1      F      Cl     H     CO.sub.2 CH.sub.3                                                                        172.5-174.5                               1      Cl     Cl     H     CH.sub.3  146.5-149                                 1      Cl     Cl     CH.sub.3                                                                             CH.sub.3  162.5-164.5                               2      F      Cl     H     H         198-200                                   2      F      Cl     H     CH.sub.3                                            2      F      Cl     CH.sub.3                                                                             CH.sub.3                                            2      F      Br     H     H                                                   2      F      Br     H     CH.sub.3                                            2      F      Br     CH.sub.3                                                                             CH.sub.3                                            2      Cl     Cl     H     H         210-212                                   2      Cl     Cl     H     CH.sub.3                                            2      Cl     Cl     CH.sub.3                                                                             CH.sub.3                                            ______________________________________                                    

                                      TABLE 2                                      __________________________________________________________________________      ##STR37##                                                                     m  R       R.sub.1                                                                              R.sub.2                                                                            R.sub.3                m.p. (°C.)                  __________________________________________________________________________     1  F       Cl    H   H                                                         1  F       Cl    H   CH.sub.2 OH            193-195                            1  F       Cl    H   CH.sub.2 OC(O)CH.sub.3 129-131                            1  F       Cl    H   CH.sub.2 OC(O)CH.sub.2 CH.sub.3                                                                       oil                                1  F       Cl    H   CH.sub.2 OC(O)CH(CH.sub.3).sub.2                                                                      oil                                1  F       Cl    H   CH.sub.2 OC(O) 1-methyl-cyclopropyl                                                                   oil                                1  F       Cl    H   CH.sub.2 OC(O)C(CH.sub.3).sub.3                                                                       oil                                1  F       Cl    H   CH.sub.2 OC(O)C.sub.6 H.sub.5                                                                         127-129                            1  F       Cl    H   CH.sub.2 OC(O)CH.sub.2 CO.sub.2 C.sub.2 H.sub.5                                                       oil                                1  F       Cl    H   CH.sub.2 OC(O)CH.sub.2 C(O)CH.sub.3                                                                   glass                              1  F       Cl    H   CH.sub.2 OC(O)NHC.sub.6 H.sub.5                                                                       glass                              1  F       Cl    H   CH.sub.2 OC(O)N(CH.sub.3)OCH.sub.3                                                                    glass                              1  F       Cl    H   CH.sub.2 OC(O)N(CH.sub.3).sub.2                           1  F       Cl    H   CH.sub.2 OC(O)CH.sub. 2 Cl                                1  F       Cl    H   CH.sub.2 OC(O)CHCHCH.sub.3                                1  F       Cl    H   CH.sub.2 OC(O)CCH                                         1  F       Cl    H   CH.sub.2 OC(O)CHC(Cl)CH.sub.3                             1  F       Cl    H   CH.sub.2 OC(O)CH.sub.2 C.sub.6 H.sub.5                    1  F       Cl    H   CH.sub.2 OC(O)CH.sub.2 CH.sub.2 C.sub.6 H.sub.5           1  F       Cl    H   CH.sub.2 OC(O)CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.3        1  F       Cl    H   CH.sub.2 CH.sub.3      103.5-106.5                        1  F       Cl    H   CH(CH.sub.3)OH         171-175                            1  F       Cl    H   CH(CH.sub.3)OC(O)CH.sub.3                                                                             136-139                            1  F       Cl    H   CH.sub.2 CH.sub.2 CH.sub.3                                1  F       Cl    H   CH(C.sub.2 H.sub.5)OH                                     1  F       Cl    H   CH(C.sub.2 H.sub.5)OC(O)CH.sub.3                          1  F       Cl    H   CH.sub.2 OSO.sub.2 CH.sub.3                               1  F       Cl    H   CH.sub.2 Br            126-130                            1  F       Cl    H   CH(CH.sub.3)Br                                            1  F       Cl    H   CH.sub.2 Cl                                               1  F       Cl    H   CH.sub.2 CH.sub.2 Cl                                      1  F       Cl    H   CH(CH.sub.3)Cl                                            1  F       Cl    H   CH.sub.2 F                                                1  F       Cl    H   CH.sub.2 (CH.sub.2).sub. 2 F                              1  F       Cl    H   CH.sub.2 CN                                               1  F       Cl    H   CH(CH.sub.3)CN                                            1  F       Cl    H   CH(NOCH.sub.3)                                            1  F       Cl    H   CH(NOCH.sub.2 CHCH.sub.2)                                 1  F       Cl    H   C(O)CH.sub.3           175-177                            1  F       Cl    H   C(NOCH.sub.2 CHCH.sub.2)CH.sub.3                                                                      glass (syn/anti mixture)           1  F       Cl    H   C(NOCH.sub.2 CO.sub.2 C.sub.2 H.sub.5)CH.sub.3            1  F       Cl    H   C(O)C.sub.6 H.sub.5                                       1  F       Cl    H   CHCH.sub.2                                                1  F       Cl    H   CCH                                                       1  F       Cl    H   COCl                   amorphous                                                                      foam                               1  F       Cl    H   CO.sub.2 H             209-211 (dec)                      1  F       Cl    H   CO.sub.2 CH.sub.3      amorphous                                                                      solid                              1  F       Cl    H   CO.sub.2 CH.sub.2 CH.sub.3                                                                            119-121                            1  F       Cl    H   CO.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                                   glass                              1  F       Cl    H   CO.sub.2 CH(CH.sub.3).sub.2                                                                           55-57                              1  F       Cl    H   CO.sub.2 (CH.sub.2).sub.3 CH.sub.3                                                                    oil                                1  F       Cl    H   CO.sub.2 CH(CH.sub.3)CH.sub.2 CH.sub.3                                                                glass                              1  F       Cl    H   CO.sub.2 CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                                                           134-135.5                          1  F       Cl    H   CO.sub.2 (CH.sub.2).sub.3 OH                                                                          glass                              1  F       Cl    H   CO.sub.2 (CH.sub.2 CH.sub.2 O).sub.2 C.sub.2                                                          oilub.5                            1  F       Cl    H   CO.sub.2 (CH.sub.2 CH.sub.2 O).sub.2 H                                                                115-120                            1  F       Cl    H   CO.sub.2 (CH.sub.2 CH.sub.2 CH.sub.2 O).sub.3                                                         glass                              1  F       Cl    H   CO.sub.2 (CH.sub.2 CH.sub.2 O).sub.6 H                                                                glass                              1  F       Cl    H   CO.sub.2 C(CH.sub.3).sub.3                                                                            glass                              1  F       Cl    H   CO.sub.2 CH.sub.2 CHCH.sub.2                                                                          104-107                            1  F       Cl    H   CO.sub.2 CH.sub.2 C(CH.sub.3)CH.sub.2                                                                 glass                              1  F       Cl    H   CO.sub.2 CH.sub.2 C(Cl)CH.sub.2                                                                       glass                              1  F       Cl    H   CO.sub.2 CH.sub.2 CCH  140-142                            1  F       Cl    H   CO.sub.2 CH.sub.2 C.sub.6 H.sub.5                                                                     138-140                            1  F       Cl    H   CO.sub.2 CH.sub.2 CO.sub.2 C.sub.2 H.sub.5                                                            58-60                              1  F       Cl    H   CO.sub.2 CH(C.sub.2 H.sub.5 )CO.sub.2 C.sub.2                                  H.sub.5                stiff oil                          1  F       Cl    H   CO.sub.2 CH(CH.sub.3)CO.sub.2 CH.sub.3                                                                glass                              1  F       Cl    H   CO.sub.2 CH(CH.sub.3)CO.sub.2 CH.sub.2 CH.sub.3                                                       foam                               1  F       Cl    H   CO.sub.2 CH.sub.2 CH.sub.2 CO.sub.2 CH.sub.3                                                          glass                              1  F       Cl    H   CO.sub.2 CH(CO.sub.2 C.sub.2 H.sub.5)CH.sub.2                                  CO.sub.2 H.sub.5       glass                              1  F       Cl    H   CO.sub.2 CH.sub.2 CH.sub.2 Si(CH.sub.3).sub.3                                                         glass                              1  F       Cl    H   CO.sub.2 CH.sub.2 CH.sub.2 Cl                             1  F       Cl    H   CO.sub.2 (CH.sub.2).sub.4 Br                              1  F       Cl    H   CN                                                        1  F       Cl    H   C(O)NH.sub.2                                              1  F       Cl    H   C(O)NH(CH.sub.3)                                          1  F       Cl    H   C(O)N(CH.sub.3).sub.2  190-193                            1  F       Cl    H   C(O)NHSO.sub.2 CH.sub.3                                   1  F       Cl    H   C(O)NHC.sub.6 H.sub.5  193-194                            1  F       Cl    H   C(O)NHCH.sub.2 CO.sub.2 C.sub.2 H.sub.5                                                               75-80                              1  F       Cl    H   C(O)NHCH(CH.sub.3)CO.sub.2 CH.sub.3                                                                   135-138                            1  F       Cl    H   C(O)NHCH(CH.sub.3)C(O)NHCH(CH.sub.3)CO.sub.2                                   CH.sub.3               foam                               1  F       Cl    H   C(O)NHCH.sub.2 CHCH.sub. 2                                1  F       Cl    H   C(O)NHCH.sub.2 CCH                                        1  F       Cl    H   C(O)N(CH.sub.3)C.sub.6 H.sub.5                            1  F       Cl    H   C(O)NHCH(CH.sub.3)C.sub.6 H.sub.5                         1  F       Cl    H   C(O)NH(CH.sub.2).sub.2 OCH.sub.2 CH.sub.3                 1  F       Cl    H   CH.sub.2 C(O)CH.sub.3                                     1  F       Cl    H   CH.sub.2 C(NOH)CH.sub.3                                   1  F       Cl    H   CH.sub.2 CH(NOC.sub.2 H.sub.5)                            1  F       Cl    H   CH(CH.sub.3)C(O)CH.sub.3                                  1  F       Cl    H   CH.sub.2 CN                                               1  F       Cl    H   CH.sub.2 CO.sub.2 H                                       1  F       Cl    H   CH.sub.2 CO.sub.2 CH.sub.3                                1  F       Cl    H   CH(CH.sub.3)CO.sub.2 CH.sub.2 CHCH.sub.2                  1  F       Cl    H   CH(CH.sub.3).sub.2                                        1  F       Cl    H   CH.sub.2 (CH.sub.2).sub.3 Br                              1  F       Cl    H   CH(CH.sub.3)CH.sub.2 CHCH.sub.2                           1  F       Cl    CH.sub.3                                                                           CH.sub.3                                                  1  F       Cl    CH.sub.3                                                                           CH.sub.2 OH                                               1  F       Cl    CH.sub.3                                                                           CH.sub.2 OC(O)CH.sub.3                                    1  F       Cl    CH.sub.3                                                                           CH.sub.2 CH.sub.3                                         1  F       Cl    CH.sub.3                                                                           CO.sub.2 H                                                1  F       Cl    CH.sub.3                                                                           CO.sub.2 CH.sub.3                                         1  F       Cl    CH.sub.3                                                                           CN                                                        1  F       Cl    CH.sub.3                                                                           CH.sub.2 C(O)CH.sub.3                                     1  F       Cl    CH.sub.3                                                                           CH.sub.2 CO.sub.2 H                                       1  F       Cl    CH.sub.3                                                                           CH.sub.2 CO.sub.2 CH.sub.3                                1  H       Cl    H   H                                                         1  H       Cl    H   CH.sub.2 OH            196-197.5                          1  H       Cl    H   CH.sub.2 OC(O)CH.sub.3 foam                               1  H       Cl    H   CH.sub.2 Br            134-136                            1  H       Cl    H   CH(NOCH.sub.2 CHCH.sub.2)                                                                             yellow oil                         1  H       Cl    H   CO.sub.2 H             220-221 (dec)                      1  H       Cl    H   CO.sub.2 CH.sub.3      121-123                            1  H       Cl    H   CO.sub.2 CH.sub.2 CH.sub.3                                                                            71-76                              1  H       Cl    H   CO.sub.2 C(CH.sub.3).sub.3                                                                            foam                               1  H       Cl    H   CO.sub.2 CH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                                                         foam                               1  H       Cl    H   CO.sub.2 NH.sub.4      197-198 (dec)                      1  H       Cl    H   CO.sub.2 NH.sub.3 CH(CH.sub.3).sub.2                                                                  211-213 (dec)                      1  H       Cl    H   CO.sub.2 Na            280-284 (dec)                      1  F       Br    H   H                                                         1  F       Br    H   CH.sub.2 OH            195-196.5                          1  F       Br    H   CH.sub.2 OC(O)CH.sub.3                                    1  F       Br    H   CH.sub.2 CH.sub.3                                         1  F       Br    H   CH.sub.2 Br                                               1  F       Br    H   C(O)CH.sub.3                                              1  F       Br    H   CH(OH)CH.sub.3                                            1  F       Br    H   CH(CH.sub.3)OC(O)CH.sub.3                                 1  F       Br    H   CO.sub.2 H             200-205                            1  F       Br    H   CO.sub.2 CH.sub.3      foam                               1  F       Br    H   COCl                   oil                                1  F       Br    H   CO.sub.2 C(CH.sub.3).sub.3                                                                            foam                               1  F       Br    H   CO.sub.2 CH.sub.2 CH.sub.2 Cl                                                                         foam                               1  F       Br    H   CN                                                        1  F       Br    H   CH(NOC.sub.2 H.sub.5)                                     1  F       Br    H   C(O)N(CH.sub.3).sub.2                                     1  F       Br    H   CH.sub.2 CO.sub.2 H                                       1  F       Br    H   CH.sub.2 CO.sub.2 C.sub.2 H.sub.5                         1  F       Br    CH.sub.3                                                                           CH.sub.3                                                  1  F       Br    CH.sub.3                                                                           CH.sub.2 OH                                               1  F       Br    CH.sub.3                                                                           CH.sub.2 OC(O)CH.sub.3                                    1  F       Br    CH.sub.3                                                                           CH.sub.2 CH.sub.3                                         1  F       Br    CH.sub.3                                                                           CO.sub.2 H                                                1  F       Br    CH.sub.3                                                                           CO.sub.2 CH.sub.3                                         1  F       Br    CH.sub.3                                                                           CH.sub.2 C(O)CH.sub.3                                     1  F       Br    CH.sub.3                                                                           CH.sub.2 CO.sub.2 H                                       1  F       Br    CH.sub.3                                                                           CH.sub.2 CO.sub.2 CH.sub.3                                1  Cl      Cl    H   CH.sub.2 OH                                               1  Cl      Cl    H   CH.sub.2 OC(O)CH.sub.3                                    1  Cl      Cl    H   CO.sub.2 H                                                1  Cl      Cl    H   CO.sub.2 CH.sub.2 CHCH.sub.2                              1  Cl      Cl    CH.sub.3                                                                           CH.sub.3               160.5-162                          1  Cl      Cl    CH.sub.3                                                                           CH.sub.2 OH                                               1  Cl      Cl    CH.sub.3                                                                           CO.sub.2 CH.sub.3                                         1  Cl      Cl    CH.sub.3                                                                           CONHCH.sub.3                                              1  H       CH.sub.3                                                                             H   CH.sub.2 OH            177-179                            1  H       CH.sub.3                                                                             H   CH.sub.2 OC(O)CH.sub.3 130-132                            1  H       CH.sub.3                                                                             H   CO.sub.2 H             229-231 (dec)                      1  H       CH.sub.3                                                                             H   CO.sub.2 CH.sub.3                                         1  H       CH.sub.3                                                                             H   CON(C.sub.2 H.sub.5).sub.2                                1  H       CH.sub.3                                                                             CH.sub.3                                                                           CH.sub.3                                                  1  H       CH.sub.3                                                                             CH.sub.3                                                                           CH.sub.2 OH                                               1  H       CH.sub.3                                                                             CH.sub.3                                                                           CO.sub.2 H                                                1  H       CH.sub.3                                                                             CH.sub.3                                                                           CO.sub.2 CH.sub.2 CCH                                     1  F       CH.sub.3                                                                             H   CH.sub.2 OH                                               1  F       CH.sub.3                                                                             H   CH.sub.2 OC(O)CH.sub.3                                    1  F       CH.sub.3                                                                             H   CO.sub.2 H                                                1  F       CH.sub.3                                                                             H   CO.sub.2 CH.sub.3                                         1  F       CH.sub.3                                                                             H   C(O)CH.sub.3                                              1  F       CH.sub.3                                                                             H   C(O)N(CH.sub.3).sub.2                                     1  F       CH.sub.3                                                                             CH.sub.3                                                                           CH.sub.3                                                  1  F       CH.sub.3                                                                             CH.sub.3                                                                           CH.sub.2 OH                                               1  F       CH.sub.3                                                                             CH.sub.3                                                                           CH.sub.2 OC(O)C.sub.2 H.sub.5                             1  F       CH.sub.3                                                                             CH.sub.3                                                                           CO.sub.2 H                                                1  F       CH.sub.3                                                                             CH.sub.3                                                                           CO.sub.2 CH.sub.2 CH.sub.3                                1  F       CH.sub.3                                                                             CH.sub.3                                                                           CH.sub.2 CH.sub.3                                         1  H       H     H   CH.sub.3               oil                                1  F       H     H   CH.sub.3                                                  1  Cl      H     H   CH.sub.3                                                  1  CH.sub.3                                                                               H     H   CH.sub.3                                                  1  C.sub.2 H.sub.5                                                                        H     H   CH.sub.3                                                  1  CH.sub.3 O                                                                             H     H   CH.sub.3                                                  1  C.sub.2 H.sub.5 O                                                                      H     H   CH.sub.3                                                  1  C.sub.3 H.sub.7 O                                                                      H     H   CH.sub.3                                                  1  (CH.sub.3).sub.2 CHO                                                                   H     H   CH.sub.3                                                  1  H       Cl    H   CH.sub.3               134-137                            1  F       Cl    H   CH.sub.3               169-171                            1  Cl      Cl    H   CH.sub.3               169.5-171                          1  CH.sub.3                                                                               Cl    H   CH.sub.3                                                  1  C.sub.2 H.sub.5                                                                        Cl    H   CH.sub.3                                                  1  CH.sub.3 O                                                                             Cl    H   CH.sub.3                                                  1  C.sub.2 H.sub.5 O                                                                      Cl    H   CH.sub.3                                                  1  C.sub.3 H.sub.7 O                                                                      Cl    H   CH.sub.3                                                  1  (CH.sub.3).sub.2 CHO                                                                   Cl    H   CH.sub.3                                                  1  H       Br    H   CH.sub.3                                                  1  F       Br    H   CH.sub.3               147-151                            1  Cl      Br    H   CH.sub.3                                                  1  CH.sub.3                                                                               Br    H   CH.sub.3                                                  1  C.sub.2 H.sub.5                                                                        Br    H   CH.sub.3                                                  1  CH.sub.3 O                                                                             Br    H   CH.sub.3                                                  1  C.sub.2 H.sub.5 O                                                                      Br    H   CH.sub.3                                                  1  C.sub.3 H.sub.7 O                                                                      Br    H   CH.sub.3                                                  1  (CH.sub.3).sub.2 CHO                                                                   Br    H   CH.sub.3                                                  1  H       CH.sub.3                                                                             H   CH.sub.3               158-160                            1  F       CH.sub.3                                                                             H   CH.sub.3                                                  1  Cl      CH.sub.3                                                                             H   CH.sub.3                                                  1  CH.sub.3                                                                               CH.sub.3                                                                             H   CH.sub.3                                                  1  C.sub.2 H.sub.5                                                                        CH.sub.3                                                                             H   CH.sub.3                                                  1  CH.sub.3 O                                                                             CH.sub.3                                                                             H   CH.sub.3                                                  1  C.sub.2 H.sub.5 O                                                                      CH.sub.3                                                                             H   CH.sub.3                                                  1  C.sub.3 H.sub.7 O                                                                      CH.sub.3                                                                             H   CH.sub.3                                                  1  (CH.sub.3).sub.2 CHO                                                                   CH.sub.3                                                                             H   CH.sub.3                                                  1  H       OCH.sub.3                                                                            H   CH.sub.3                                                  1  F       OCH.sub.3                                                                            H   CH.sub.3                                                  1  Cl      OCH.sub.3                                                                            H   CH.sub.3                                                  1  CH.sub.3                                                                               OCH.sub.3                                                                            H   CH.sub.3                                                  1  C.sub.2 H.sub.5                                                                        OCH.sub.3                                                                            H   CH.sub.3                                                  1  CH.sub.3 O                                                                             OCH.sub.3                                                                            H   CH.sub.3                                                  1  C.sub.2 H.sub.5 O                                                                      OCH.sub.3                                                                            H   CH.sub.3                                                  1  C.sub.3 H.sub.7 O                                                                      OCH.sub.3                                                                            H   CH.sub.3                                                  1  (CH.sub.3).sub.2 CHO                                                                   OCH.sub.3                                                                            H   CH.sub.3                                                  1  H       CN    H   CH.sub.3                                                  1  F       CN    H   CH.sub.3                                                  1  Cl      CN    H   CH.sub.3                                                  1  CH.sub.3                                                                               CN    H   CH.sub.3                                                  1  C.sub.2 H.sub.5                                                                        CN    H   CH.sub.3                                                  1  CH.sub.3 O                                                                             CN    H   CH.sub.3                                                  1  C.sub.2 H.sub.5 O                                                                      CN    H   CH.sub.3                                                  1  C.sub.3 H.sub.7 O                                                                      CN    H   CH.sub.3                                                  1  (CH.sub.3).sub.2 CHO                                                                   CN    H   CH.sub.3                                                  1  H       CF.sub.3                                                                             H   CH.sub.3                                                  1  F       CF.sub.3                                                                             H   CH.sub.3                                                  1  Cl      CF.sub.3                                                                             H   CH.sub.3                                                  1  CH.sub.3                                                                               CF.sub.3                                                                             H   CH.sub.3                                                  1  C.sub.2 H.sub.5                                                                        CF.sub.3                                                                             H   CH.sub.3                                                  1  CH.sub.3 O                                                                             CF.sub.3                                                                             H   CH.sub.3                                                  1  C.sub.2 H.sub.5 O                                                                      CF.sub.3                                                                             H   CH.sub. 3                                                 1  C.sub.3 H.sub.7 O                                                                      CF.sub.3                                                                             H   CH.sub.3                                                  1  (CH.sub.3).sub.2 CHO                                                                   CF.sub.3                                                                             H   CH.sub.3                                                  1  H       OCF.sub.3                                                                            H   CH.sub.3                                                  1  F       OCF.sub.3                                                                            H   CH.sub.3                                                  1  Cl      OCF.sub.3                                                                            H   CH.sub.3                                                  1  CH.sub.3                                                                               OCF.sub.3                                                                            H   CH.sub.3                                                  1  C.sub.2 H.sub.5                                                                        OCF.sub.3                                                                            H   CH.sub.3                                                  1  CH.sub.3 O                                                                             OCF.sub.3                                                                            H   CH.sub.3                                                  1  C.sub.2 H.sub.5 O                                                                      OCF.sub.3                                                                            H   CH.sub.3                                                  1  C.sub.3 H.sub.7 O                                                                      OCF.sub.3                                                                            H   CH.sub.3                                                  1  (CH.sub.3).sub.2 CHO                                                                   OCF.sub.3                                                                            H   CH.sub.3                                                  1  H       OCF.sub.2 H                                                                          H   CH.sub.3                                                  1  F       OCF.sub.2 H                                                                          H   CH.sub.3                                                  1  Cl      OCF.sub.2 H                                                                          H   CH.sub.3                                                  1  CH.sub.3                                                                               OCF.sub.2 H                                                                          H   CH.sub.3                                                  1  C.sub.2 H.sub.5                                                                        OCF.sub.2 H                                                                          H   CH.sub.3                                                  1  CH.sub.3 O                                                                             OCF.sub.2 H                                                                          H   CH.sub.3                                                  1  C.sub.2 H.sub.5 O                                                                      OCF.sub.2 H                                                                          H   CH.sub.3                                                  1  C.sub.3 H.sub.7 O                                                                      OCF.sub.2 H                                                                          H   CH.sub.3                                                  1  (CH.sub.3).sub.2 CHO                                                                   OCF.sub.2 H                                                                          H   CH.sub.3                                                  2  F       Cl    H   CH.sub.2 OH                                               2  F       Cl    H   CH.sub.2 OC(O)CH.sub.3                                    2  F       Cl    H   CH.sub.2 CH.sub.3                                         2  F       Cl    H   CH(CH.sub.3)OH                                            2  F       Cl    H   CH(CH.sub.3)OC(O)CH.sub.3                                 2  F       Cl    H   CH.sub.2 Br                                               2  F       Cl    H   C(O)CH.sub.3                                              2  F       Cl    H   C(NOCH.sub.2 CHCH.sub.2)CH.sub.3                          2  F       Cl    H   CO.sub.2 H                                                2  F       Cl    H   CO.sub.2 CH.sub.3                                         2  F       Cl    H   CN                                                        2  F       Cl    H   C(O)N(CH.sub.3).sub.2                                     2  F       Cl    H   C(O)NHSO.sub.2 CH.sub.3                                   2  F       Cl    CH.sub.3                                                                           CH.sub.3                                                  2  F       Cl    CH.sub.3                                                                           CH.sub.2 OC(O)CH.sub.3                                    2  F       Cl    CH.sub.3                                                                           CO.sub.2 H                                                2  F       Cl    CH.sub.3                                                                           CO.sub.2 CH.sub.3                                         2  F       Cl    CH.sub.3                                                                           CN                                                        2  F       Cl    CH.sub.3                                                                           C.sub.2 H.sub.5                                           2  F       Br    H   H                                                         2  F       Br    H   CH.sub.3                                                  2  F       Br    H   CH.sub.2 OH                                               2  F       Br    H   CH.sub.2 OC(O)CH.sub.3                                    2  F       Br    H   CH.sub.2 CH.sub.3                                         2  F       Br    H   CH(CH.sub.3)OH                                            2  F       Br    H   CH(CH.sub.3)OC(O)CH.sub.3                                 2  F       Br    H   CH.sub.2 Br                                               2  F       Br    H   C(O)CH.sub.3                                              2  F       Br    H   C(NOCH.sub.2 CHCH.sub.2)CH.sub.3                          2  F       Br    H   CO.sub.2 H                                                2  F       Br    H   CO.sub.2 CH.sub.3                                         2  F       Br    H   CN                                                        2  F       Br    H   C(O)N(CH.sub.3).sub.2                                     2  F       Br    H   C(O)NHSO.sub.2 CH.sub.3                                   2  F       Br    CH.sub.3                                                                           CH.sub.3                                                  2  F       Br    CH.sub.3                                                                           CH.sub.2 OC(O)CH.sub.3                                    2  F       Br    CH.sub.3                                                                           CO.sub.2 H                                                2  F       Br    CH.sub.3                                                                           CO.sub.2 CH.sub.3                                         2  F       Br    CH.sub.3                                                                           CN                                                        2  F       Br    CH.sub.3                                                                           C.sub.2 H.sub.5                                           2  Cl      Cl    H   H                      191-193                            2  Cl      Cl    H   CH.sub.3                                                  2  Cl      Cl    H   CH.sub.2 OH                                               2  Cl      Cl    H   CH.sub.2 OC(O)CH.sub.3                                    2  Cl      Cl    H   CH.sub.2 CH.sub.3                                         2  Cl      Cl    H   CH(CH.sub.3)OH                                            2  Cl      Cl    H   CH(CH.sub.3)OC(O)CH.sub.3                                 2  Cl      Cl    H   CH.sub.2 Br                                               2  Cl      Cl    H   C(O)CH.sub.3                                              2  Cl      Cl    H   C(NOCH.sub.2 CHCH.sub.2)CH.sub.3                          2  Cl      Cl    H   CO.sub.2 H                                                2  Cl      Cl    H   CO.sub.2 CH.sub.3                                         2  Cl      Cl    H   CN                                                        2  Cl      Cl    H   C(O)N(CH.sub.3).sub.2                                     2  Cl      Cl    H   C(O)NHSO.sub.2 CH.sub.3                                   2  Cl      Cl    CH.sub.3                                                                           CH.sub.3                                                  2  Cl      Cl    CH.sub.3                                                                           CH.sub.2 OC(O)CH.sub.3                                    2  Cl      Cl    CH.sub.3                                                                           CO.sub.2 H                                                2  Cl      Cl    CH.sub.3                                                                           CO.sub.2 CH.sub.3                                         2  Cl      Cl    CH.sub.3                                                                           CN                                                        2  Cl      Cl    CH.sub.3                                                                           C.sub.2 H.sub.5                                           __________________________________________________________________________

                  TABLE 3                                                          ______________________________________                                          ##STR38##                                                                      ##STR39##                                                                     m    X      Y      R    R.sub.1                                                                             R.sub.2                                                                              R.sub.3 m.p. (°C.)                   ______________________________________                                         1    S      S      H    Cl   H     CH.sub.3                                                                               glass                               1    S      S      F    Cl   CH.sub.3                                                                             CH.sub.3                                    1    S      S      Cl   Cl   H     CO.sub.2 CH.sub.3                           1    S      S      F    Br   H     CH.sub.3                                    1    S      O      H    Cl   H     CH.sub.3                                                                               foam                                1    S      O      F    Cl   CH.sub.3                                                                             CH.sub.3                                    1    S      O      Cl   Cl   H     CO.sub.2 CH.sub.3                           1    S      O      F    Br   H     CH.sub.3                                    2    S      S      F    Cl   H     H                                           2    S      O      F    Br   H     CH.sub.3                                    ______________________________________                                    

                  TABLE 4                                                          ______________________________________                                          ##STR40##                                                                      ##STR41##                                                                     15 m R      R.sub.1                                                                               R.sub.2                                                                             R.sub.3        m.p. (°C.)                       ______________________________________                                         1    F      Cl     H    H                                                      1    F      Cl     H    CH.sub.3       glass                                   1    F      Cl     H    CH.sub.2 OH    75-77                                   1    F      Cl     H    CH.sub.2 OC(O)CH.sub.3                                                                        oil                                     1    F      Cl     H    CH.sub.2 CH.sub.3                                      1    F      Cl     H    CH(CH.sub.3)OH                                         1    F      Cl     H    CH(CH.sub.3)OC(O)CH.sub.3                              1    F      Cl     H    CH.sub.2 Br    144-146                                 1    F      Cl     H    C(O)CH.sub.3                                           1    F      Cl     H    C(NOCH.sub.2 CHCH.sub.2)CH.sub.3                       1    F      Cl     H    CO.sub.2 H     oil                                     1    F      Cl     H    CO.sub.2 CH.sub.3                                                                             oil                                     1    F      Cl     H    CN                                                     1    F      Cl     H    C(O)N(CH.sub.3).sub.2                                  1    F      Cl     H    C(O)NHSO.sub.2 CH.sub.3                                1    F      Cl     CH.sub.3                                                                            CH.sub.3                                               1    F      Cl     CH.sub.3                                                                            CH.sub.2 OC(O)CH.sub.3                                 1    F      Cl     CH.sub.3                                                                            CO.sub.2 H                                             1    F      Cl     CH.sub.3                                                                            CO.sub.2 CH.sub.3                                      1    F      Cl     CH.sub.3                                                                            CN                                                     1    F      Cl     CH.sub.3                                                                            C.sub.2 H.sub.5                                        2    F      Cl     H    H                                                      2    F      Cl     H    CH.sub.3                                               2    F      Cl     H    CH.sub.2 OH                                            2    F      Cl     H    CH.sub.2 OC(O)CH.sub.3                                 2    F      Cl     H    CH.sub.2 CH.sub.3                                      2    F      Cl     H    CH(CH.sub.3)OH                                         2    F      Cl     H    CH(CH.sub.3)OC(O)CH.sub.3                              2    F      Cl     H    CH.sub.2 Br                                            2    F      Cl     H    C(O)CH.sub.3                                           2    F      Cl     H    C(NOCH.sub.2 CHCH.sub.2)CH.sub.3                       2    F      Cl     H    CO.sub.2 H                                             2    F      Cl     H    CO.sub.2 CH.sub.3                                      2    F      Cl     H    CN                                                     2    F      Cl     H    C(O)N(CH.sub.3).sub.2                                  2    F      Cl     H    C(O)NHSO.sub.2 CH.sub.3                                2    F      Cl     CH.sub.3                                                                            CH.sub.3                                               2    F      Cl     CH.sub.3                                                                            CH.sub.2 OC(O)CH.sub.3                                 2    F      Cl     CH.sub.3                                                                            CO.sub.2 H                                             2    F      Cl     CH.sub.3                                                                            CO.sub.2 CH.sub.3                                      2    F      Cl     CH.sub.3                                                                            CN                                                     2    F      Cl     CH.sub.3                                                                            C.sub.2 H.sub.5                                        ______________________________________                                    

                  TABLE 5                                                          ______________________________________                                          ##STR42##                                                                      ##STR43##                                                                     n      R     R.sub.1                                                                              R.sub.2                                                                             R.sub.3        m.p. (°C.)                       ______________________________________                                         1      F     Cl    H    H                                                      1      F     Cl    H    CH.sub.3       158-159                                 1      F     Cl    H    CH.sub.2 OH    236-238                                 1      F     Cl    H    CH.sub.2 OC(O)CH.sub.3                                                                        stiff oil                               1      F     Cl    H    CH.sub.2 CH.sub.3                                      1      F     Cl    H    CH(CH.sub.3)OH                                         1      F     Cl    H    CH(CH.sub.3)OC(O)CH.sub.3                              1      F     Cl    H    CH.sub.2 Br                                            1      F     Cl    H    C(O)CH.sub.3                                           1      F     Cl    H    C(NOCH.sub.2 CHCH.sub.2)CH.sub.3                       1      F     Cl    H    CO.sub.2 H     239-241                                 1      F     Cl    H    CO.sub.2 CH.sub.3                                                                             foam                                    1      F     Cl    H    CO.sub.2 C(CH.sub.3).sub.3                                                                    foam                                    1      F     Cl    H    CN                                                     1      F     Cl    H    C(O)N(CH.sub.3).sub.2                                                                         foam                                    1      F     Cl    H    C(O)NHSO.sub.2 CH.sub.3                                1      F     Cl    H    C(O)Cl         foam                                    1      F     Cl    CH.sub.3                                                                            CH.sub.3                                               1      F     Cl    CH.sub.3                                                                            CH.sub.2 OH                                            1      F     Cl    CH.sub.3                                                                            CH.sub.2 OC(O)CH(CH.sub.3).sub.2                       1      F     Cl    CH.sub.3                                                                            CO.sub.2 H                                             1      F     Cl    CH.sub.3                                                                            CO.sub.2 CH.sub.3                                      1      F     Cl    CH.sub.3                                                                            CN                                                     1      F     Cl    CH.sub.3                                                                            C(O)NH(CH.sub.3)                                       1      F     Cl    CH.sub.3                                                                            C.sub.2 H.sub.5                                        1      Cl    Cl    H    H                                                      1      Cl    Cl    H    CH.sub.3       198-202                                 1      Cl    Cl    H    CH.sub.2 OH                                            1      Cl    Cl    H    CH.sub.2 OC(O)CH.sub.3                                 1      Cl    Cl    H    CH.sub.2 CH.sub.3                                      1      Cl    Cl    H    CH(CH.sub.3)OH                                         1      Cl    Cl    H    CH(CH.sub.3)OC(O)CH.sub.3                              1      Cl    Cl    H    CH.sub.2 Br                                            1      Cl    Cl    H    C(O)CH.sub.3                                           1      Cl    Cl    H    C(NOCH.sub.2 CHCH.sub.2)CH.sub.3                       1      Cl    Cl    H    CO.sub.2 H                                             1      Cl    Cl    H    CO.sub.2 CH.sub.3                                      1      Cl    Cl    H    CO.sub.2 C(CH.sub.3).sub.3                             1      Cl    Cl    H    CN                                                     1      Cl    Cl    H    C(O)N(CH.sub.3).sub.2                                  1      Cl    Cl    H    C(O)NHSO.sub.2 CH.sub.3                                1      Cl    Cl    CH.sub.3                                                                            CH.sub.3                                               1      Cl    Cl    CH.sub.3                                                                            CH.sub.2 OH                                            1      Cl    Cl    CH.sub.3                                                                            CH.sub.2 OC(O)CH.sub.3                                 1      Cl    Cl    CH.sub.3                                                                            CO.sub.2 H                                             1      Cl    Cl    CH.sub.3                                                                            CO.sub.2 CH.sub.3                                      1      Cl    Cl    CH.sub.3                                                                            CN                                                     ______________________________________                                         n   m      R     R.sub.1                                                                            R.sub.2                                                                             R.sub.3        m.p. (°C.)                     ______________________________________                                         1   1      Cl    Cl  CH.sub.3                                                                            C(O)NH(CH.sub.3)                                     1   1      Cl    Cl  CH.sub.3                                                                            C.sub.2 H.sub.5                                      1   1      F     Br  H    H                                                    1   1      F     Br  H    CH.sub.3                                             1   1      F     Br  H    CH.sub.2 OH                                          1   1      F     Br  H    CH.sub.2 OC(O)CH.sub.3                               1   1      F     Br  H    CH.sub.2 CH.sub.3                                    1   1      F     Br  H    CO.sub.2 H                                           1   1      F     Br  H    CO.sub.2 CH.sub.3                                    1   1      F     Br  H    C(O)N(CH.sub.3).sub.2                                1   1      F     Br  CH.sub.3                                                                            CH.sub.3                                             1   1      F     Br  CH.sub.3                                                                            CH.sub.2 OC(O)CH.sub. 3                              1   1      F     Br  CH.sub.3                                                                            CO.sub.2 CH.sub.3                                    1   1      F     Br  CH.sub.3                                                                            CONH(CH.sub.3)                                       1   1      H     Cl  H    CH.sub.3       170.5-172                             2   1      F     Cl  H    CH.sub.3                                             2   1      Cl    Cl  H    CH.sub.3                                             2   1      H     Cl  H    CH.sub.3       148-150                               2   1      F     Br  H    CH.sub.3                                             2   1      F     Cl  CH.sub.3                                                                            CH.sub.3                                             2   1      Cl    Cl  CH.sub.3                                                                            CH.sub.3                                             2   1      H     Cl  CH.sub.3                                                                            CH.sub.3                                             2   1      F     Br  CH.sub.3                                                                            CH.sub.3                                             1   2      Cl    Cl  H    H              221-224                               1   2      Cl    Cl  H    CH.sub.3                                             1   2      Cl    Cl  H    CH.sub.2 OH                                          1   2      Cl    Cl  H    CH.sub.2 OC(O)CH.sub.3                               1   2      Cl    Cl  H    CH.sub.2 CH.sub.3                                    1   2      Cl    Cl  H    CH.sub.2 Br                                          1   2      Cl    Cl  H    C(O)CH.sub.3                                         1   2      Cl    Cl  H    CO.sub.2 H                                           1   2      Cl    Cl  H    CO.sub.2 CH.sub.3                                    1   2      Cl    Cl  H    CO.sub.2 C(CH.sub.3).sub.3                           1   2      Cl    Cl  H    CN                                                   1   2      Cl    Cl  H    C(O)N(CH.sub.3).sub.2                                1   2      Cl    Cl  H    C(O)NHSO.sub.2 CH.sub. 3                             1   2      Cl    Cl  CH.sub.3                                                                            CH.sub.3                                             1   2      Cl    Cl  CH.sub.3                                                                            CH.sub.2 OH                                          1   2      Cl    Cl  CH.sub.3                                                                            CO.sub.2 H                                           1   2      Cl    Cl  CH.sub.3                                                                            CO.sub.2 CH.sub.3                                    1   2      Cl    Cl  CH.sub.3                                                                            CN                                                   1   2      Cl    Cl  CH.sub.3                                                                            C(O)NH(CH.sub.3)                                     1   2      Cl    Cl  CH.sub.3                                                                            C.sub.2 H.sub.5                                      1   2      F     Br  H    H                                                    1   2      F     Br  H    CH.sub.3                                             1   2      F     Br  H    CH.sub.2 OH                                          1   2      F     Br  H    CH.sub.2 OC(O)CH.sub.3                               1   2      F     Br  H    CH.sub.2 CH.sub.3                                    1   2      F     Br  H    CO.sub.2 H                                           1   2      F     Br  H    CO.sub.2 CH.sub.3                                    1   2      F     Br  H    C(O)N(CH.sub.3).sub.2                                1   2      F     Br  CH.sub.3                                                                            CH.sub.3                                             1   2      F     Br  CH.sub.3                                                                            CH.sub.2 OC(O)CH.sub.3                               1   2      F     Br  CH.sub.3                                                                            CO.sub.2 CH.sub.3                                    1   2      F     Br  CH.sub.3                                                                            CONH(CH.sub.3)                                       1   2      H     Cl  H    CH.sub.3                                             2   2      F     Cl  H    CH.sub.3                                             2   2      Cl    Cl  H    CH.sub.3                                             2   2      H     Cl  H    CH.sub.3                                             2   2      F     Br  H    CH.sub.3                                             2   2      F     Cl  CH.sub.3                                                                            CH.sub.3                                             2   2      Cl    Cl  CH.sub.3                                                                            CH.sub.3                                             2   2      H     Cl  CH.sub.3                                                                            CH.sub.3                                             2   2      F     Br  CH.sub.3                                                                            CH.sub.3                                             1   2      F     Cl  H    H              178-180                               1   2      F     Cl  H    CH.sub.3                                             1   2      F     Cl  H    CH.sub.2 OH                                          1   2      F     Cl  H    CH.sub.2 OC(O)CH.sub.3                               1   2      F     Cl  H    CH.sub.2 CH.sub.3                                    1   2      F     Cl  H    CH.sub.2 Br                                          1   2      F     Cl  H    C(O)CH.sub.3                                         1   2      F     Cl  H    CO.sub.2 H                                           1   2      F     Cl  H    CO.sub.2 CH.sub.3                                    1   2      F     Cl  H    CO.sub.2 C(CH.sub.3).sub.3                           1   2      F     Cl  H    CN                                                   1   2      F     Cl  H    C(O)N(CH.sub.3).sub.2                                1   2      F     Cl  H    C(O)NHSO.sub.2 CH.sub.3                              1   2      F     Cl  CH.sub.3                                                                            CH.sub.3                                             1   2      F     Cl  CH.sub.3                                                                            CH.sub.2 OH                                          1   2      F     Cl  CH.sub.3                                                                            CO.sub.2 H                                           1   2      F     Cl  CH.sub.3                                                                            CO.sub.2 CH.sub.3                                    1   2      F     Cl  CH.sub.3                                                                            CN                                                   1   2      F     Cl  CH.sub.3                                                                            C(O)NH(CH.sub.3)                                     1   2      F     Cl  CH.sub.3                                                                            C.sub.2 H.sub.5                                      ______________________________________                                    

                  TABLE 5a                                                         ______________________________________                                          ##STR44##                                                                      ##STR45##                                                                     m     n       R       R.sub.1                                                                              R.sub.2                                                                              R.sub.3                                                                               m.p. (°C.)                     ______________________________________                                         1     1       F       Cl    H     H                                            1     1       F       Cl    H     CH.sub.3                                     1     1       F       Cl    H     CH.sub.2 OH                                  1     1       F       Cl    H     CO.sub.2 CH.sub.3                            1     1       F       Cl    CH.sub.3                                                                             CH.sub.3                                     2     1       F       Cl    H     H                                            2     1       F       Cl    H     CH.sub.3                                     2     1       F       Cl    H     CH.sub.2 OH                                  2     1       F       Cl    H     CO.sub.2 CH.sub.3                            2     1       F       Cl    CH.sub.3                                                                             CH.sub.3                                     1     2       F       Cl    H     H                                            1     2       F       Cl    H     CH.sub.3                                     1     2       F       Cl    H     CH.sub.2 OH                                  1     2       F       Cl    H     CO.sub.2 CH.sub.3                            1     2       F       Cl    CH.sub.3                                                                             CH.sub.3                                     2     2       F       Cl    H     H                                            2     2       F       Cl    H     CH.sub.3                                     2     2       F       Cl    H     CH.sub.2 OH                                  2     2       F       Cl    H     CO.sub.2 CH.sub.3                            2     2       F       Cl    CH.sub.3                                                                             CH.sub.3                                     1     1       Cl      Cl    H     H                                            1     1       Cl      Cl    H     CH.sub.3                                     1     1       Cl      Cl    H     CH.sub.2 OH                                  1     1       Cl      Cl    H     CO.sub.2 CH.sub.3                            1     1       Cl      Cl    CH.sub.3                                                                             CH.sub.3                                     2     1       Cl      Cl    H     H                                            2     1       Cl      Cl    H     CH.sub.3                                     2     1       Cl      Cl    H     CH.sub.2 OH                                  2     1       Cl      Cl    H     CO.sub.2 CH.sub.3                            2     1       Cl      Cl    CH.sub.3                                                                             CH.sub.3                                     1     2       Cl      Cl    H     H                                            1     2       Cl      Cl    H     CH.sub.3                                     1     2       Cl      Cl    H     CH.sub.2 OH                                  1     2       Cl      Cl    H     CO.sub.2 CH.sub.3                            1     2       Cl      Cl    CH.sub.3                                                                             CH.sub.3                                     2     2       Cl      Cl    H     H                                            2     2       Cl      Cl    H     CH.sub.3                                     2     2       Cl      Cl    H     CH.sub.2 OH                                  2     2       Cl      Cl    H     CO.sub.2 CH.sub.3                            2     2       Cl      Cl    CH.sub.3                                                                             CH.sub.3                                     1     1       F       Br    H     H                                            1     1       F       Br    H     CH.sub.3                                     1     1       F       Br    H     CH.sub.2 OH                                  1     1       F       Br    H     CO.sub.2 CH.sub.3                            1     1       F       Br    CH.sub.3                                                                             CH.sub.3                                     2     1       F       Br    H     H                                            2     1       F       Br    H     CH.sub.3                                     2     1       F       Br    H     CH.sub.2 OH                                  2     1       F       Br    H     CO.sub.2 CH.sub.3                            2     1       F       Br    CH.sub.3                                                                             CH.sub.3                                     1     2       F       Br    H     H                                            1     2       F       Br    H     CH.sub.3                                     1     2       F       Br    H     CH.sub.2 OH                                  1     2       F       Br    H     CO.sub.2 CH.sub.3                            1     2       F       Br    CH.sub.3                                                                             CH.sub.3                                     2     2       F       Br    H     H                                            2     2       F       Br    H     CH.sub.3                                     2     2       F       Br    H     CH.sub.2 OH                                  2     2       F       Br    H     CO.sub.2 CH.sub.3                            2     2       F       Br    CH.sub.3                                                                             CH.sub.3                                     ______________________________________                                    

                  TABLE 6                                                          ______________________________________                                          ##STR46##                                                                      ##STR47##                                                                     m      R      R.sub.1                                                                               R.sub.2                                                                              R.sub.3    m.p. (°C.)                        ______________________________________                                         1      H      Cl     H     CH.sub.3   125-127                                  1      F      Cl     H     H                                                   1      F      Cl     H     CH.sub.3   glass                                    1      F      Cl     H     CH.sub.2 OC(O)CH.sub.3                              1      F      Cl     H     CO.sub.2 CH.sub.3                                   1      F      Cl     CH.sub.3                                                                             CH.sub.3                                            2      F      Cl     H     H          131-133                                  2      F      Cl     H     CH.sub.3                                            2      F      Cl     H     CH.sub.2 OC(O)CH.sub.3                              2      F      Cl     H     CO.sub.2 CH.sub.3                                   2      F      Cl     CH.sub.3                                                                             CH.sub.3                                            1      F      Br     H     H                                                   1      F      Br     H     CH.sub.3                                            1      F      Br     CH.sub.3                                                                             CH.sub.3                                            2      F      Br     H     H                                                   2      F      Br     H     CH.sub. 3                                           2      F      Br     CH.sub.3                                                                             CH.sub.3                                            ______________________________________                                    

                  TABLE 7                                                          ______________________________________                                          ##STR48##                                                                      ##STR49##                                                                     m    R      R.sub.1                                                                               R.sub.2                                                                             R.sub.3    m.p. (°C.)                           ______________________________________                                         1    H      Cl     H    CH.sub.3   145-148                                     1    Cl     Cl     H    CH.sub.3   182-185 (Isomer 1)                          1    Cl     Cl     H    CH.sub.3   206-108 (Isomer 2)                          1    Cl     Cl     CH.sub.3                                                                            CH.sub.3                                               1    F      Cl     H    CH.sub.3   150-152                                     1    F      Cl     H    CH.sub.2 OC(O)CH.sub.3                                 1    F      Cl     H    CO.sub.2 CH.sub.3                                                                         foam                                        1    F      Cl     CH.sub.3                                                                            CH.sub.3                                               1    F      Br     H    CH.sub.3                                               1    F      Br     CH.sub.3                                                                            CH.sub.3                                               2    F      Cl     H    H          169-172 (Isomer 1)                          2    F      Cl     H    H          161-163 (Isomer 2)                          2    F      Cl     H    CH.sub.3                                               2    F      Cl     CH.sub.3                                                                            CH.sub.3                                               2    Cl     Cl     H    H          204-208 (Isomer 1)                          2    Cl     Cl     H    H          209-211 (Isomer 2)                          2    Cl     Cl     H    CH.sub.3                                               2    Cl     Cl     CH.sub.3                                                                            CH.sub.3                                               2    F      Br     H    H                                                      2    F      Br     H    CH.sub.3                                               2    F      Br     CH.sub.3                                                                            CH.sub.3                                               ______________________________________                                    

                  TABLE 8                                                          ______________________________________                                          ##STR50##                                                                      ##STR51##                                                                     m      W       R       R.sub.1                                                                              R.sub.2                                                                              R.sub.3                                                                              (m.p. (°C.)                    ______________________________________                                         1      S       F       Cl    H     H                                           1      S       F       Cl    H     CH.sub.3                                    1      S       F       Cl    CH.sub.3                                                                             CH.sub.3                                    1      S       Cl      Cl    H     H                                           1      S       Cl      Cl    H     CH.sub.3                                    1      S       Cl      Cl    CH.sub.3                                                                             CH.sub.3                                    1      S       F       Br    H     H                                           1      S       F       Br    H     CH.sub.3                                    1      S       F       Br    CH.sub.3                                                                             CH.sub.3                                    1      SO.sub.2                                                                               F       Cl    H     CH.sub.3                                    1      SO.sub.2                                                                               Cl      Cl    H     H                                           1      SO.sub.2                                                                               F       Br    CH.sub.3                                                                             CH.sub.3                                    2      S       F       Cl    H     H                                           2      S       Cl      Cl    H     CH.sub.3                                    2      S       F       Br    CH.sub.3                                                                             CH.sub.3                                    2      SO.sub.2                                                                               F       Cl    H     CH.sub.3                                    2      SO.sub.2                                                                               Cl      Cl    H     H                                           2      SO.sub.2                                                                               F       Br    CH.sub.3                                                                             CH.sub.3                                    ______________________________________                                    

                  TABLE 9                                                          ______________________________________                                          ##STR52##                                                                      ##STR53##                                                                     m    n      R      R.sub.1                                                                             R.sub.2                                                                              R.sub.3   m.p. (°C.)                      ______________________________________                                         1    1      H      Cl   H     CH.sub.3  175-177                                1    1      Cl     Cl   H     CH.sub.3  201.5-203.5                            1    1      Cl     Cl   CH.sub.3                                                                             CH.sub.3                                         1    1      F      Cl   H     CH.sub.3    192-194.5                            1    1      F      Cl   CH.sub.3                                                                             CH.sub.3                                         1    1      F      Cl   H     CO.sub.2 (CH.sub.2).sub.4 Br                                                             oil                                    1    1      F      Cl   H     CO.sub.2 CH.sub.3                                                                        glass                                  1    1      F      Br   H     CH.sub.3                                         1    1      F      Br   CH.sub.3                                                                             CH.sub.3                                         2    1      F      Cl   H     H         185-188                                2    1      F      Cl   H     CH.sub.3                                         2    1      F      Cl   CH.sub.3                                                                             CH.sub.3                                         2    1      Cl     Cl   H     H         210-214                                2    1      Cl     Cl   H     CH.sub.3                                         2    1      Cl     Cl   CH.sub.3                                                                             CH.sub.3                                         2    1      F      Br   H     H                                                2    1      F      Br   H     CH.sub.3                                         2    1      F      Br   CH.sub.3                                                                             CH.sub.3                                         1    2      F      Cl   H     CH.sub.3                                         1    2      F      Cl   CH.sub.3                                                                             CH.sub.3                                         1    2      Cl     Cl   H     CH.sub.3                                         1    2      Cl     Cl   CH.sub.3                                                                             CH.sub.3                                         1    2      F      Br   H     CH.sub.3                                         1    2      F      Br   CH.sub.3                                                                             CH.sub.3                                         2    2      F      Cl   H     H         174-178                                2    2      F      Cl   H     CH.sub.3                                         2    2      F      Cl   CH.sub.3                                                                             CH.sub.3                                         2    2      Cl     Cl   H     H         149-153                                2    2      Cl     Cl   H     CH.sub.3                                         2    2      Cl     Cl   CH.sub.3                                                                             CH.sub.3                                         2    2      F      Br   H     H                                                2    2      F      Br   H     CH.sub.3                                         2    2      F      Br   CH.sub.3                                                                             CH.sub.3                                         ______________________________________                                    

                  TABLE 10                                                         ______________________________________                                          ##STR54##                                                                      ##STR55##                                                                     m   n     R     R.sub.1                                                                            R.sub.2                                                                             R.sub.3    R.sub.9                                                                               m.p. (°C.)                   ______________________________________                                         1   2     F     Cl  H    CH.sub.3   F                                          1   2     F     Cl  H    CH.sub.3   Cl                                         1   2     F     Cl  H    CH.sub.3   Br                                         1   2     F     Cl  H    CH.sub.3   CH.sub.3                                   1   2     F     Cl  H    CH.sub.3   CN                                         1   2     F     Cl  H    CH.sub.3   OCH.sub.3                                  1   2     F     Cl  H    CH.sub.3   SCH.sub.3                                  1   2     F     Cl  H    CH.sub.3   SO.sub.2 CH.sub.3                          1   1     F     Cl  H    CH.sub.3   Cl                                         1   1     F     Cl  H    CH.sub.3   Br                                         1   1     F     Cl  H    CH.sub.3   CN                                         1   2     H     Cl  H    CH.sub.3   Cl     oil                                 1   2     F     Cl  H    CH.sub.3   Cl     glass                               1   2     F     Cl  H    CH.sub.2 OC(O)CH.sub.3                                                                    Cl                                         1   2     F     Cl  H    CO.sub.2 CH.sub.3                                                                         Cl                                         1   2     F     Cl  H    C(O)N(CH.sub.3).sub.2                                                                     Cl                                         1   2     F     Cl  CH.sub.3                                                                            CH.sub.3   Br                                         1   2     F     Br  H    CH.sub.3   Cl                                         1   2     F     Br  H    C.sub.2 H.sub.5                                                                           Br                                         1   2     F     Br  H    CH.sub.2 OH                                                                               Cl                                         1   2     F     Br  H    CO.sub.2 CH.sub.3                                                                         Cl                                         1   2     F     Br  CH.sub.3                                                                            CH.sub.3   Br                                         2   1     F     Cl  H    H          Cl                                         2   1     F     Cl  H    H          Br                                         2   1     F     Cl  H    H          CN                                         2   2     F     Cl  H    H          Cl                                         2   2     F     Cl  H    H          Br                                         2   2     F     Cl  H    H          CN                                         2   2     F     Cl  H    CH.sub.3   Cl                                         2   2     F     Cl  H    C.sub.2 H.sub.5                                                                           Br                                         2   2     F     Cl  H    CH.sub.2 OC(O)CH.sub.3                                                                    Cl                                         2   2     F     Cl  H    CO.sub.2 C.sub.2 H.sub.5                                                                  CN                                         2   2     F     Cl  CH.sub.3                                                                            CH.sub.3   Cl                                         2   2     F     Br  H    H          Cl                                         2   2     F     Br  H    CH.sub.3   Br                                         2   2     F     Br  CH.sub.3                                                                            CH.sub.3   CN                                         ______________________________________                                    

                  TABLE 11                                                         ______________________________________                                          ##STR56##                                                                      ##STR57##                                                                     m    R      R.sub.1                                                                               R.sub.2                                                                             R.sub.3                                                                              R.sub.10   m.p. (°C.)                     ______________________________________                                         1    F      Cl     H    CH.sub.3                                                                             CH.sub.3                                         1    F      Cl     H    CH.sub.3                                                                             C.sub.2 H.sub.5                                  1    F      Cl     H    CH.sub.3                                                                             C.sub.3 H.sub.7                                  1    F      Cl     H    CH.sub.3                                                                             CH(CH.sub.3).sub.2                               1    F      Cl     H    CH.sub.3                                                                             C.sub.4 H.sub.9                                  1    F      Cl     H    CH.sub.3                                                                             CH.sub.2 CH(CH.sub.3).sub.2                      1    F      Cl     H    CH.sub.3                                                                             CH(CH.sub.3)C.sub.2 H.sub.5                      1    F      Cl     H    CH.sub.3                                                                             C(CH.sub.3).sub.3                                1    F      Cl     H    CH.sub.3                                                                             CH.sub.2 F                                       1    F      Cl     H    CH.sub.3                                                                             CH.sub.2 CH.sub.2 Br                             1    F      Cl     H    CH.sub.3                                                                             CH.sub.2 CH.sub.2 CH.sub.2 Cl                    1    F      Cl     H    CH.sub.3                                                                             (CH.sub.2).sub.3 CH.sub.2 F                      1    H      Cl     H    CH.sub.3                                                                             C(CH.sub.3).sub.3                                                                         79-81                                 1    Cl     Cl     H    CH.sub.3                                                                             C(CH.sub.3).sub.3                                                                         112-115                               1    F      Br     H    CH.sub.3                                                                             C(CH.sub.3).sub.3                                ______________________________________                                    

                  TABLE 12                                                         ______________________________________                                          ##STR58##                                                                      ##STR59##                                                                     m       R       R.sub.1 R.sub.2                                                                              R.sub.3                                                                               m.p. (°C.)                         ______________________________________                                         1       H       Cl      H     CH.sub.3                                                                              188-191                                   1       F       Cl      H     CH.sub.3                                                                              124.5-126.5                               1       F       Cl      H     CH.sub.2 OH                                      1       F       Cl      H     CO.sub.2 CH.sub.3                                1       F       Cl      CH.sub.3                                                                             CH.sub.3                                         1       F       Br      H     CH.sub.3                                         1       F       Br      H     CO.sub.2 CH.sub.3                                2       F       Cl      H     H                                                2       F       Br      H     H                                                ______________________________________                                    

                  TABLE 13                                                         ______________________________________                                          ##STR60##                                                                     m       R       R.sub.1 R.sub.2                                                                               R.sub.3                                                                               m.p. (°C.)                        ______________________________________                                         1       H       Cl      H      CH.sub.3                                                                              semi-solid                               1       F       Cl      H      CH.sub.3                                        1       F       Br      CH.sub.3                                                                              CH.sub.3                                        ______________________________________                                    

                  TABLE 14                                                         ______________________________________                                          ##STR61##                                                                      ##STR62##                                                                                                                  m.p.                              m   R     R.sub.1                                                                              R.sub.2                                                                             R.sub.3                                                                               R.sub.8 R.sub.10 (°C.)                      ______________________________________                                         1   H     Cl    H    CH.sub.3                                                                              CH.sub.3                                                                               CF.sub.2 H                                                                              122.5-                                                                         123.5                             1   F     Cl    H    CH.sub.3                                                                              Cl      (CH.sub.2).sub.3 CH.sub.3                  1   F     Cl    H    CH.sub.3                                                                              CH.sub.3                                                                               CF.sub.2 H                                 1   F     Cl    H    CH.sub.3                                                                              C.sub.2 H.sub.5                                                                        (CH.sub.2).sub.2 CH.sub.3                  1   F     Cl    H    CH.sub.3                                                                              C.sub.3 H.sub.7                                                                        C.sub.2 H.sub.5                            1   F     Cl    H    CH.sub.3                                                                              C(CH.sub. 3).sub.3                                                                     CH.sub.3                                   1   F     Cl    H    CH.sub.3                                                                              CF.sub.2 H                                                                             CF.sub.2 CHClF                             1   F     Cl    H    CH.sub.3                                                                              CH.sub.2 CH.sub.2 Cl                                                                   (CH.sub.2).sub.3 F                         1   F     Cl    H    CH.sub.3                                                                              (CH.sub.2).sub.3 F                                                                     (CH.sub.3).sub.4 Br                        1   Cl    Cl    CH.sub.3                                                                            CH.sub.3                                                                              CH.sub.3                                                                               CF.sub.2 H                                 1   F     Br    H    CO.sub.2 CH.sub.3                                                                     CH.sub.3                                                                               CF.sub.2 H                                 2   F     Cl    H    H      CH.sub.3                                                                               CF.sub.2 H                                 2   Cl    Cl    H    CH.sub.3                                                                              CH.sub.3                                                                               CF.sub.2 H                                 2   F     Br    CH.sub.3                                                                            CH.sub.3                                                                              CH.sub.3                                                                               CF.sub.2 H                                 ______________________________________                                    

                  TABLE 15                                                         ______________________________________                                          ##STR63##                                                                      ##STR64##                                                                     m   R     R.sub.1                                                                               R.sub.2                                                                             R.sub.3    R.sub.10                                                                               m.p. (°C.)                     ______________________________________                                         1   F     Cl     H    CH.sub.3   CH.sub.3                                      1   F     Cl     H    CH.sub.3   C.sub.2 H.sub.5                               1   F     Cl     H    CH.sub.3   C.sub.3 H.sub.7                               1   F     Cl     H    CH.sub.3   CH(CH.sub.3).sub.2                            1   F     Cl     H    CH.sub.3   C.sub.4 H.sub.9                               1   F     Cl     H    CH.sub.3   CF.sub.2 H                                    1   F     Cl     H    CH.sub.3   CH.sub.2 CH.sub.2 Br                          1   F     Cl     H    CH.sub.3   (CH.sub.2).sub.3 F                            1   F     Cl     H    CH.sub.3   (CH.sub.2).sub.4 Cl                           1   F     Cl     H    CO.sub.2 CH.sub. 3                                                                        (CH.sub.2).sub.3 F                            1   F     Cl     CH.sub.3                                                                            CH.sub.3   (CH.sub.2).sub.3 F                            1   Cl    Cl     H    C.sub.2 H.sub.5                                                                           (CH.sub.2).sub.3 F                            1   F     Br     H    CH.sub.2 OC(O)CH.sub.3                                                                    (CH.sub.2).sub.3 F                            2   F     Cl     H    H          (CH.sub.2).sub.3 F                            2   Cl    Cl     CH.sub.3                                                                            CH.sub.3   (CH.sub.2).sub.3 F                            2   F     Br     H    CO.sub.2 CH.sub.3                                                                         (CH.sub.2).sub.3 F                            2   F     Cl     H    H          CF.sub.2 H                                    2   Cl    CL     CH.sub.3                                                                            CH.sub.3   CF.sub.2 H                                    2   F     Br     H    CO.sub.2 CH.sub.3                                                                         CF.sub.2 H                                    ______________________________________                                    

                  TABLE 16                                                         ______________________________________                                          ##STR65##                                                                      ##STR66##                                                                     m   R     R.sub.1                                                                              R.sub.2                                                                             R.sub.3    R.sub.10 m.p. (°C.)                     ______________________________________                                         1   H     Cl    H    CH.sub.3   CH.sub.3 131-132                               1   F     Cl    H    CH.sub.3   C.sub.2 H.sub.5                                1   F     Cl    H    CH.sub.3   C.sub.3 H.sub.7                                1   F     Cl    H    CH.sub.3   CH(CH.sub.3).sub.2                             1   F     Cl    H    CH.sub.3   C.sub.4 H.sub.9                                1   F     Cl    H    CH.sub.3   CH.sub.2 F                                     1   F     Cl    H    CH.sub.3   CH.sub.2 CH.sub.2 Br                           1   F     Cl    H    CH.sub.3   (CH.sub.2).sub.3 F                             1   F     Cl    H    CH.sub.3   (CH.sub.2).sub.4 Cl                            1   F     Cl    H    CH.sub.3   CH.sub.3                                       1   F     Cl    H    CH.sub.2 OC(O)CH.sub.3                                                                    CH.sub.3                                       1   F     Cl    CH.sub.3                                                                            CH.sub.3   CH.sub.3                                       1   Cl    Cl    H    CO.sub.2 CH.sub.3                                                                         CH.sub.3                                       1   F     Br    H    C.sub.2 H.sub.5                                                                           CH.sub.3                                       2   F     Cl    H    H          CH.sub.3                                       2   Cl    Cl    H    CH.sub.3   CH.sub.3                                       2   F     Br    H    CO.sub.2 CH.sub.3                                                                         CH.sub.3                                       ______________________________________                                    

                  TABLE 17                                                         ______________________________________                                          ##STR67##                                                                      ##STR68##                                                                     m       R       R.sub.1 R.sub.2                                                                               R.sub.3                                                                               m.p. (°C.)                        ______________________________________                                         1       F       Cl      H      CH.sub.3                                        1       Cl      Cl      H      C.sub.2 H.sub.5                                 1       F       Br      CH.sub.3                                                                              CH.sub.3                                        2       F       Cl      H      H                                               ______________________________________                                    

                  TABLE 18                                                         ______________________________________                                          ##STR69##                                                                     m       R       R.sub.1 R.sub.2                                                                               R.sub.3                                                                               m.p. (°C.)                        ______________________________________                                         1       F       Cl      H      CH.sub.3                                        1       Cl      Cl      H      C.sub.2 H.sub.5                                 1       F       Br      CH.sub.3                                                                              CH.sub.3                                        2       F       Cl      H      H                                               ______________________________________                                    

                  TABLE 19                                                         ______________________________________                                          ##STR70##                                                                      ##STR71##                                                                     m       R       R.sub.1 R.sub.2                                                                               R.sub.3 m.p. (°C.)                       ______________________________________                                         1       H       H       H      H       127-128                                 1       F       Cl      H      CH.sub.3                                        1       Cl      Cl      CH.sub.3                                                                              CH.sub.3                                        1       F       Br      H      CO.sub.2 CH.sub.3                               2       F       Cl      H      H                                               2       Cl      Cl      H      CH.sub.3                                        2       F       Br      CH.sub.3                                                                              CH.sub.3                                        ______________________________________                                          ##STR72##                                                                     m       R       R.sub.1 R.sub.2                                                                               R.sub.3 m.p. (°C.)                       ______________________________________                                         1       F       Cl      H      CH.sub.3                                        1       Cl      Cl      CH.sub. 3                                                                             CH.sub.3                                        1       F       Br      H      CO.sub.2 CH.sub.3                               2       F       Cl      H      H                                               2       Cl      Cl      H      CH.sub.3                                        2       F       Br      CH.sub.3                                                                              CH.sub.3                                        ______________________________________                                    

                  TABLE 20                                                         ______________________________________                                          ##STR73##                                                                      ##STR74##                                                                     m       R       R.sub.1 R.sub.2                                                                               R.sub.3 m.p. (°C.)                       ______________________________________                                         1       H       H       H      CH3     114-118                                 1       F       H       H      CH.sub.3                                        1       F       H       CH.sub.3                                                                              CH.sub.3                                        1       F       H       H      CO.sub.2 CH.sub.3                               2       F       H       H      H                                               2       F       H       H      H                                               2       F       H       H      CH.sub.3                                        2       F       H       CH.sub.3                                                                              CH.sub.3                                        ______________________________________                                          ##STR75##                                                                     m       R       R.sub.1 R.sub.2                                                                               R.sub.3 m.p. (°C.)                       ______________________________________                                         1       F       H       H      CH.sub.3                                        1       Cl      H       CH.sub.3                                                                              CH.sub.3                                        1       F       H       H      CO.sub.2 CH.sub.3                               2       F       H       H      H                                               2       Cl      H       H      CH.sub.3                                        2       F       H       CH.sub.3                                                                              CH.sub.3                                        ______________________________________                                    

                  TABLE 21                                                         ______________________________________                                          ##STR76##                                                                      ##STR77##                                                                     m      R      R.sub.1                                                                               R.sub.2                                                                              R.sub.3    m.p. (°C.)                        ______________________________________                                         1      H      H      H     H          165-167                                  1      H      H      CH.sub.3                                                                             CH.sub.3   144-146                                  1      H      H      H     CH.sub.3   140-143                                  1      H      H      H     CH.sub.2 OH                                                                               140-145                                  1      H      H      H     CO.sub.2 C(CH.sub.3).sub.3                                                                yellow foam                              1      H      H      H     CO.sub.2 H 179-181                                  1      H      H      H     CO.sub.2 CH.sub.3                                                                         yellow foam                              1      H      H      H     CON(CH.sub.3).sub.2                                                                       yellow foam                              1      H      H      H     CH.sub.2 OC(O)CH.sub.3                                                                    142-144                                  1      F      H      H     CH.sub.3                                            1      F      H      CH.sub.3                                                                             CH.sub.3                                            2      F      H      H     H                                                   2      F      H      H     CH.sub.3                                            2      F      H      CH.sub.3                                                                             CH.sub.3                                            ______________________________________                                          ##STR78##                                                                     m      R      R.sub.1 R.sub.2                                                                             R.sub.3    m.p. (°C.)                        ______________________________________                                         1      F      H       H    CH.sub.3                                            1      Cl     H       CH.sub.3                                                                            CH.sub.3                                            1      F      H       H    CO.sub.2 CH.sub.3                                   2      F      H       H    H                                                   2      Cl     H       H    CH.sub.3                                            2      F      H       CH.sub.3                                                                            CH.sub.3                                            ______________________________________                                    

Formulations

Useful formulations of the compounds of Formula I can be prepared in conventional ways. They include dusts, granules, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates and the like. Many of these may be applied directly. Sprayable formulations can be extended in suitable media and used at spray volumes of from a few liters to several hundred liters per hectare. High strength compositions are primarily used as intermediates for further formulation. The formulations, broadly, contain about 0.1% to 99% by weight of active ingredient(s) and at least one of (a) about 0.1% to 20% surfactant(s) and (b) about 1% to 99.9% solid or liquid diluent(s). More specifically, they will contain these ingredients in the following approximate proportions:

                  TABLE 22                                                         ______________________________________                                                     Active  Weight Percent*                                                        Ingredient                                                                             Diluent(s)                                                                               Surfactant(s)                                    ______________________________________                                         Wettable Powders                                                                             20-90     0-74      1-10                                         Oil Suspensions,                                                                             3-50      40-95     0-15                                         Emulsions, Solutions,                                                          (including Emulsifiable                                                        Concentrates)                                                                  Aqueous Suspension                                                                           10-50     40-84     1-20                                         Dusts         1-25      70-99     0-5                                          Granules and Pellets                                                                         0.1-95    5-99.9    0-15                                         High Strength 90-99     0-10      0-2                                          Compositions                                                                   ______________________________________                                          *Active ingredient plus at least one of a Surfactant or a Diluent equals       100 weight percent.   Lower or higher levels of active ingredient can, of      course, be present depending on the intended use and the physical      properties of the compound. Higher ratios of surfactant to active      ingredient are sometimes desirable, and are achieved by incorporation into      the formulation or by tank mixing.

Typical solid diluents are described in Watkins, et al., "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Dorland Books, Caldwell, N.J., but other solids, either mined or manufactured, may be used. The more absorptive diluents are preferred for wettable powders and the denser ones for dusts. Typical liquid diluents and solvents are described in Marsden, "Solvents Guide," 2nd Ed., Interscience, New York, 1950. Solubility under 0.1% is preferred for suspension concentrates; solution concentrates are preferably stable against phase separation at 0° C. "McCutcheon's Detergents and Emulsifier Annual", MC Publishing Corp., Ridgewood, N.J., as well as Sisely and Wood, "Encyclopedia of Surface Active Agents", Chemical Publishing Co., Inc., New York, 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foaming, caking, corrosion, microbiological growth, etc.

The methods of making such compositions are well known. Solutions are prepared by simply mixing the ingredients. Fine solid compositions are made by blending and, usually, grinding as in a hammer or fluid energy mill. Suspensions are prepared by wet milling (see, for example, Littler, U.S. Pat. No. 3,060,084). Granules and pellets may be made by spraying the active material upon preformed granular carriers or by agglomeration techniques. See J. E. Browning, "Agglomeration", Chemical Engineering, Dec. 4, 1967, pp. 147ff. and "Perry's Chemical Engineer's Handbook", 5th Ed., McGraw-Hill, New York, 1973, pp. 8-57ff.

For further information regarding the art of formulation, see for example:

H. M. Loux, U.S. Pat. No. 3,235,361 Feb. 15, 1966, Col. 6, line 16 through Col. 7, line 19 and Examples 10 through 41;

R. W. Luckenbaugh, U.S. Pat. No. 3,309,192, Mar. 14, 1967, Col. 5, line 43 through Col. 7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182;

H. Gysin and E. Knusli, U.S. Pat. No. 2,891,855, June 23, 1959, Col. 3, line 66 through Col. 5, line 17 and Examples 1-4;

G. C. Klingman, "Weed Control as a Science", John Wiley and Sons, Inc., New York, 1961, pp. 81-96; and

J. D. Fryer and S. A. Evans, "Weed Control Handbook", 5th Ed., Blackwell Scientific Publications, Oxford, 1968, pp. 101-103.

In the following examples, all parts are by weight unless otherwise indicated.

EXAMPLE A Wettable Powder

    ______________________________________                                         ((1,2,4))triazolo((4,3-A))pyridin-3(2H)--one, 2-                               (5,7-dichloro-2,3-dihydro-2-methyl-4-benzofuranyl)-                            5,6,7,8-tetrahydro         80%                                                 sodium alkylnaphthalenesulfonate                                                                          2%                                                  sodium ligninsulfonate     2%                                                  synthetic amorphous silica 3%                                                  kaolinite                  13%                                                 ______________________________________                                    

The ingredients are blended, hammer-milled until all the solids are essentially under 50 microns, reblended, and packaged.

EXAMPLE B Low Strength Granule

    ______________________________________                                         ((1,2,4))triazolo((4,3-A))pyridin-3(2H)--one, 2-                               (5,7-dichloro-2,3-dihydro-2-methyl-4-benzofuranyl)-                            5,6,7,8-tetrahydro         1%                                                  N,N--dimethylformamide     9%                                                  attapulgite granules       90%                                                 (U.S.S. 20-40 sieve)                                                           ______________________________________                                    

The active ingredient is dissolved in the solvent and the solution is sprayed upon dedusted granules in a double cone blender. After spraying of the solution has been completed, the blender is allowed to run for a short period and then the granules are packaged.

EXAMPLE C

    ______________________________________                                         ((1,2,4))triazolo((4,3-A))pyridin-3(2H)--one, 2-                               (5,7-dichloro-2,3-dihydro-2-methyl-4-benzofuranyl)-                            5,6,7,8-tetrahydro         40%                                                 polyacrylic acid thickener 0.3%                                                dodecylphenol polyethylene glycol ether                                                                   0.5%                                                disodium phosphate         1%                                                  monosodium phosphate       0.5%                                                polyvinyl alcohol          1.0%                                                water                      56.7%                                               ______________________________________                                    

The ingredients are blended and ground together in a sand mill to produce particles essentially all under 5 microns in size.

EXAMPLE D Granule

    ______________________________________                                         ((1,2,4))triazolo((4,3-A))pyridin-3(2H)--one, 2-                               (5,7-dichloro-2,3-dihydro-2-methyl-4-benzofuranyl)-                            5,6,7,8-tetrahydro         80%                                                 wetting agent              1%                                                  crude ligninsulfonate salt (containing                                                                    10%                                                 5-20% of the natural sugars)                                                   attapulgite clay           9%                                                  ______________________________________                                    

The ingredients are blended and milled to pass through a 100 mesh screen. This material is then added to a fluid bed granulator, the air flow is adjusted to gently fluidize the material, and a fine spray of water is sprayed onto the fluidized material. The fluidization and spraying are continued until granules of the desired size range are made. The spraying is stopped, but fluidization is continued, optionally with heat, until the water content is reduced to the desired level, generally less than 1%. The material is then discharged, screened to the desired size range, generally 14-100 mesh (1410-149 microns), and packaged for use.

EXAMPLE E High Strength Concentrate

    ______________________________________                                         ((1,2,4))triazolo((4,3-A))pyridin-3(2H)--one, 2-                               (5,7-dichloro-2,3-dihydro-2-methyl-4-benzofuranyl)-                            5,6,7,8-tetrahydro         99%                                                 silica aerogel             0.5%                                                synthetic amorphous silica 0.5%                                                ______________________________________                                    

The ingredients are blended and ground in a hammer-mill to produce a material essentially all passing a U.S.S. No. 50 screen (0.3 mm opening). The concentrate may be formulated further if necessary.

EXAMPLE F Extruded Pellet

    ______________________________________                                         ((1,2,4))triazolo((4,3-A))pyridin-3(2H)--one, 2-                               (5,7-dichloro-2,3-dihydro-2-methyl-4-benzofuranyl)-                            5,6,7,8-tetrahydro         25%                                                 anhydrous sodium sulfate   10%                                                 crude calcium ligninsulfonate                                                                             5%                                                  sodium alkylnaphthalenesulfonate                                                                          1%                                                  calcium/magnesium bentonite                                                                               59%                                                 ______________________________________                                    

The ingredients are blended, hammer-milled and then moistened with about 12% water. The mixture is extruded as cylinders about 3 mm diameter which are cut to produce pellets about 3 mm long. These may be crushed to pass a U.S.S. No. 10 sieve (0.84 mm openings). The granules held on a U.S.S. No. 40 sieve (0.42 mm openings) may be packaged for use and the fines recycled.

EXAMPLE G Oil Suspension

    ______________________________________                                         ((1,2,4))triazolo((4,3-A))pyridin-3(2H)--one, 2-                               (5,7-dichloro-2,3-dihydro-2-methyl-4-benzofuranyl)-                            5,6,7,8-tetrahydro         25%                                                 polyoxyethylene sorbitol hexoleate                                                                        5%                                                  highly aliphatic hydrocarbon oil                                                                          70%                                                 ______________________________________                                    

The ingredients are ground together in a sand mill until the solid particles have been reduced to under about 5 microns. The resulting thick suspension may be applied directly, but preferably after being extended with oils or emulsified in water.

EXAMPLE H Dust

    ______________________________________                                         ((1,2,4))triazolo((4,3-A))pyridin-3(2H)--one, 2-                               (5,7-dichloro-2,3-dihydro-2-methyl-4-benzofuranyl)-                            5,6,7,8-tetrahydro         10%                                                 attapulgite                10%                                                 pyrophyllite               80%                                                 ______________________________________                                    

The active ingredient in blended with attapulgite and then passed through a hammer-mill to produce particles substantially all below 200 microns. The ground concentrate is then blended with powdered pyrophyllite until homogeneous.

EXAMPLE I Emulsifiable Concentrate

    ______________________________________                                         ((1,2,4))triazolo((4,3-A))pyridin-3(2H)--one, 2-                               (5,7-dichloro-2,3-dihydro-2-methyl-4-benzofuranyl)-                            5,6,7,8-tetrahydro         20%                                                 chlorobenzene              74%                                                 sorbitan monostearate and                                                      polyoxyethylene condensates thereof                                                                       6%                                                  ______________________________________                                    

The ingredients are combined and stirred to produce a solution which can be emulsified in water for application.

Utility

Test results indicate that the compounds of the present invention are active herbicides. They hae utility for broad-spectrum pre- and/or post-emergence weed control in areas where complete control of all vegetation is desired, such as around industrial storage areas, parking lots, drive-in theaters, around billboards, highway and railroad structures. Some of the compounds have utility for selective weed control in crops such as rice, wheat, barley, corn, soybeans, sugarbeets and cotton. Alternatively, the subject compounds are useful to modify plant growth.

The rates of application for the compounds of the invention are determined by a number of factors, including their use as selective or general herbicides, the crop species involved, the types of weeds to be controlled, weather and climate, formulations selected, mode of application, amount of foliage present, etc. In general terms, the subject compounds should be applied at levels of around 0.001 to 20 kg/ha, the lower rates being suggested for use on lighter soils and/or those having a low organic matter content, for plant growth modification or for situations where only short-term persistence is required, such as a herbicide for fallow land.

The compounds of the invention may be used in combination with any other commercial herbicide, non-limiting examples of which are listed below.

    ______________________________________                                         Common Name                                                                              Chemical Name                                                        ______________________________________                                         acetochlor                                                                               2-chloro-B--(ethoxymethyl)-N--(2-ethyl-                                        6-methylphenyl)acetamide                                             acifluorfen                                                                              5-[2-chloro-4-(trifluoromethyl)phenoxy]-                                       2-nitrobenzoic acid                                                  acrolein  2-propenal                                                           alachlor  2-chloro-2,6-diethylphenyl-N--(methoxy                                         methyl)acetanilide                                                   ametryn   N--ethyl-N'--1(1-methylethyl)-6-(methyl-                                       thio)-1,3,5-triazine-2,4-diamine                                     amitrole  1H--1,2,4-triazol-3-amine                                            AMS       ammonium sulfamate                                                   asulam    methyl [(4-amiophenyl)sulfonyl]carbamate                             atrazine  6-chloro-N--ethyl-N'--(1methylethyl)-1,3,5-                                    triazine-2,4-diamine                                                 barban    4-chloro-2-butynyl 3-chlorophenylcarbamate                           benefin   N--butyl-N--ethyl-2,6-dinitro-4-(tri-                                          fluoromethyl)benzenamine                                             bensulfuron                                                                              2-methyl-[[[[[(4,6-dimethoxy-2-pyrimidinyl)-                         methyl    amino]carbonyl]amino]sulfonyl]methyl]-                                         benzoic acid, methyl ester                                           bensulide O,O--bis(1-methylethyl) S--[2-[(phenylsulfonyl)-                               amino]ethyl] phosphorodithioate                                      bentazon  3-(1-methylethyl)-(1H)--2,1,3-benzothiadiazin0                                 4(3H)--one, 2,2-dioxide                                              benzofluor                                                                               N--[4-(ethylthio)-2-(trifluoromethyl)phenyl]-                                  methanesulfonamide                                                   benzoylprop                                                                              N--benzoyl-N--(3,4-dichlorophenyl)-DL-                                         alaine                                                               bifenox   methyl 5-(2,4-dich1orophenoxy)-2-                                              nitrobenzoate                                                        bromacil  5-bromo-6-methyl-3-(1-methylpropyl)-2,4-                                       (1H,3H)pyrimidinedione                                               bromoxynil                                                                               3,5-dibromo-4-hydroxybenzonitrile                                    butachlor N--(butoxymethyl)-2-chloro-N--(2,6-diethyl-                                    phenyl)acetamide                                                     buthidazole                                                                              3-[5-(1,1-dimethylethyl)-1,3,4-thiadia-                                        zol-2-yl]-4-hydroxy-1-methyl-2-imida-                                          zolidinone                                                           butralin  4-(1,1-dimethylethyl)-N--(1-methyl-                                            propyl)-2,6-dinitrobenzenamine                                       butylate  S--ethyl-bis(2-methylpropyl)carbamothioate                           cacodylic dimethyl arsinic acid                                                acid                                                                           CDAA      2-chloro-N,N--di-2-propenylacetamide                                 CDEC      2-chloroallyl diethyldithiocarbamate                                 chloramben                                                                               3-amino-2,5-dichlorobenzoic acid                                     chlorbromuron                                                                            3-(4-bromo-3-chlorophenyl)-1-methoxy-1-                                        methylurea                                                           chlorimuron                                                                              2-[[[[(4-chloro-6-methoxy-2-pyrimidinyl)-                            ethyl     amino]carbonyl]amino]sulfonyl]benzoic-                                         acid, ethyl ester                                                    chloroxuron                                                                              N'--[4-(4-chlorophenoxy)phenyl]-N,N--                                          dimethylurea                                                         chlorpropham                                                                             1-methylethyl 3-chlorophenylcarbamate                                chlorsulfuron                                                                            2-chloro-N--[(4-methoxy-6-methyl-1,3,5-                                        triazin-2-yl)amino]carbonyl]benzene-                                           sulfonamide                                                          chlortoluron                                                                             N'--(3-chloro-4-methylphenyl)-N,N--                                            dimethylurea                                                         cinmethylin                                                                              exo-1-methyl-4-(1-methylethyl)-2-                                              [(2-methylphenyl)methoxy]-7-                                                   oxabicyclo[2.2.1]heptane                                             clethodim (E,E)-(±)-2-[[(3-chloro-2-propenyl)oxy]-                                    imino]propyl]-5-[2-(ethylthio)-propyl]-                                        3-hydroxy-2-cyclohexan-1-one                                         clomazone 2-[(2-chlorophenyl)methyl]-4,4-dimethyl-                                       3-isoxazolidinone                                                    cloproxydim                                                                              (E,E)-2-[1-[[(3-chloro-2-propenyl)oxy)                                         imino]butyl]-5-[2-(ethylthio)propyl]-                                          3-hydroxy-2-cyclohexen-1-one                                         clopyralid                                                                               3,6-dichloro-2-pyridinecarboxylic acid                               CMA       calcium salt of MAA                                                  cyanazine 2-[[4-chloro-6-(ethylamino)-1,3,5-                                             triazin-2-yl]amino]-2-methyl-                                                  propanenitrile                                                       cycloate  S--ethyl cyclohexylethylcarbamothioate                               cycluron  3-cyclooctyl-1,1-dimethylurea                                        cyperquat 1-methyl-4-phenylpyridinium                                          cyprazine 2-chloro-4-(cyclopropylamino)-6-(iso-                                          propylamino)- .sub.-s-triazine                                       cyprazole N--[5-(2-chloro-1,1-dimethylethyl)-1,3,4-                                      thiadiazol-2-yl]cyclopropanecarbox-                                            amide                                                                cypromid  3',4'-dichlorocyclopropanecarboxanilide                              dalapon   2,2-dichloropropionic acid                                           dalapon   2,2-dichloropropanoic acid                                           dazomet   tetrahydro-3,5-dimethyl-2H--1,3,5-thia-                                        diazine-2-thione                                                     DCPA      dimethyl 2,3,5,6-tetrachloro-1,4-                                              benzenedicarboxylate                                                 desmediphan                                                                              ethyldesmetryn[3-[[(phenylamino)-                                              carbonyl]oxy]phenyl]carbamate                                        desmetryn 2-(isopropylamino)-4-(methylamino)-6-                                          methylthio)- .sub.-s-triazine                                        diallate  S--(2,3-dichloro-2-propenyl) bis(1-methyl-                                     ethyl)carbamothioate                                                 dicamba   3,6-dichloro-2-methoxybenzoic acid                                   dichlobenil                                                                              2,6-dichlorobenzonitrile                                             dichlorprop                                                                              (±)-2-(2,4-dichlorophenoxy)propanoic                              acid                                                                           diclofop  (±)-2-[4-(2,4-dichlorophenoxy)phenoxy]-                                     propanoic acid                                                       diethatyl N--(chloroacetyl)-N--(2,6-diethylphenyl)-                                      glycine                                                              difenzoquat                                                                              1,2-dimethyl-3,5-diphenyl-1H--pyrazolium                             dinitramine                                                                              N.sup.3,N.sup.3 --diethyl-2,4-dinitro-6-(tri-                                  fluoromethyl)-1,3-benzenediamine                                     dinoseb   2-(1-methylpropyl)-4,6-dinitrophenol                                 diphenamide                                                                              N,N--dimethyl-α-phenylbenzeneacetamide                         dipropetryn                                                                              6-(ethylthio)-N,N'--bis(1-methylethyl)-                                        1,3,5-triazine-2,4-diamine                                           diquat    6,7-dihydrodipyrido[1,2-a:2',1'-c]-                                            pyrazinediium ion                                                    diuron    N'--(3,4-dichlorophenyl)-N,N--dimethylurea                           DNOC      2-methyl-4,6-dinitrophenol                                           DPX-M6316 3-DSMA[[[[(4-methoxy-6-methyl-1,3,5-                                           triazin-2-yl)amino]carbonyl]amino]-                                            sulfonyl]-2-thiophenecarboxylic acid,                                          methyl ester                                                         DSMA      disodium salt of MAA                                                 endothall 7-oxabicyclo[2.2.1]heptane-2,3-dicarbox-                                       ylic acid                                                            EPTC      S--ethyl dipropylcarbamothioate                                      ethafluralin                                                                             N--ethyl-N--(2-methyl-2-propenyl)-2,6-                                         dinitro-4-(trifluoromethyl)benzen-                                             amine                                                                ethofumesate                                                                             (±)-2-ethoxy-2,3-dihydro-3,3-dimethyl-                                      5-benzofuranyl methanesulfonate                                      Express ®                                                                            2-[[[[N--(4-methoxy-6-methyl-                                                  1,3,5-triazine-2-yl)-N--methylamino]-                                          carbonyl]amino]sulfonyl]benzoic acid,                                          methyl ester                                                         fenac     2,3,6-trichlorophenylacetic acid                                     fenoxaprop                                                                               (±)-2-[4-[6-chloro-2-benzoxazolyl-                                          oxy]phenoxy]propanoic acid                                           fenuron   N,N--dimethyl-N'--phenylurea                                         fenuron TCA                                                                              Salt of fenuron and TCA                                              flamprop  N--benzoyl-N--(3-chloro-4-fluorophenyl)-                                       DL-alanine                                                           fluazifop (±)-2-[4-[[5-(trifluoromethyl)-2-                                           pyridinyl]oxy]phenoxy]propanoic                                                acid                                                                 fluazifop-P                                                                              (R)--  2-[4-[[5-(trifluoromethyl)-2-                                           pyridiny1]oxy]phenoxy]propanoic                                                acid                                                                 fluchloralin                                                                             N--(2-chloroethyl)-2,6-dinitro-N--propyl-                                      4-(trifluoromethyl)benzenamine                                       fluometuron                                                                              N,N--dimethyl-N'--[3-trifluoromethyl)                                          phenyl]urea                                                          fluoro-   3-chloro-4-(chloromethyl)-1-[3-                                      chloridone                                                                               (trifluoromethyl)phenyl]-2-pyrroli-                                            dinone                                                               fluorodifen                                                                               -p-nitrophenyl a,a,a-trifluoro-2-nitro-                                        -p-tolyl ether                                                      fluorogly-                                                                               carboxymethyl 5-[2-chloro-4-(tri-                                    cofen     fluoromethyl)phenoxy]-2-nitro-                                                 benzoate                                                             fluridone 1-methyl-3-phenyl-5-[3-(trifluoro-                                             methyl)phenyl]-4(1H)--pyridinone                                     fomesafen 5-[2-chloro-4-trifluoromethyl)phenoxy]-                                        N--(methylsulfonyl)-2-nitrobenzamide                                 fosamine  ethyl hydrogen (aminocarbonyl)phosphate                              glyphosate                                                                               N--(phosphonomethyl)glycine                                          halozyfop 2-[4-[[3-chloro-5-(trifluoromethyl)-                                           2-pyridinyl]oxy]phenoxy]propanoic                                              acid                                                                 hexaflurate                                                                              potassium hexafluoroarsenate                                         hexazinone                                                                               3-cyclohexyl-6-(dimethylamino)-1-methyl-                                       1,3,5-triazine-2,4(1H,3H)--dione                                     imazametha-                                                                              6-(4-isopropyl-4-methyl-5-oxo-2-                                     benz      imidazolin-2-yl)- -p-toluic acid,                                              methyl ester                                                         imazapyr  (±)-[4,5-dihydro-4-methyl-4-(1-methyl-                                      ethyl)-5-oxo-1H--imidazol-2-yl]-3-                                             pyridinecarboxylic acid                                              imazaquin 2-[4,5-dihydro-4-methyl-4-(1-methyl-                                           ethyl)-5-oxo-1H--imidazol-2-yl]-3-                                             quinolinecarboxylic acid                                             imazethapyr                                                                              (±)-2-[4,5-dihydro-4-methyl-4-(1-methyl                                     ethyl)-5-oxo-1H--imidazol-2-yl]-5-                                             ethyl-3-pyridinecarboxylic acid                                      ioxynil   4-hydroxy-3,5-diiodobenzonitrile                                     isopropalin                                                                              4-(1-methylethyl)-2,6-dinitro-N,N--                                            dipropylbenzenamine                                                  isoproturon                                                                              N--(4-isopropylphenyl)-N',N'--dimethylurea                           isouron   N'--[(1,1-dimethylethyl)-3-isoxazolyl]-                                        N,N--dimethylurea                                                    isoxaben  N--[3-(1-ethyl-1-methylpropyl)-5-                                              isoxazolyl]-2,6-dimethoxybenzamide                                   karbutilate                                                                              3-[[(dimethylamino)carbonyl]amino]-                                            phenyl (1,1-dimethylethyl)-                                                    carbamate                                                            lactofen  (±)-2-ethoxy-1-methyl-2-oxoethyl 5-[2-                                      chloro-4-(trifluoromethyl)phenoxy]-                                            2-nitrobenzoate                                                      lenacil   3-cyclohexyl-6,7-dihydro-1H--cyclopenta-                                       pyrimidine-2,4(3H,5H)-dione                                          linuron   N'--(3,4-dichlorophenyl)-N--methoxy-N--                                        methylurea                                                           MAA       methylarsonic acid                                                   MAMA      monoammonium salt of MAA                                             MCPA      (4-chloro-2-methylphenoxy)acetic acid                                MCPB      4-(4-chloro-2-methylphenoxy)butanoic                                           acid                                                                 mecoprop  (±)-2-(4-chloro-2-methylphenoxy)-                                           propanoic acid                                                       mefluidide                                                                               N--[2,4-dimethyl-5-[[(trifluoromethyl)-                                        sulfonyl]amino]phenyl]acetamide                                      methal-   N--(2-methyl-2-propenyl)-2,6-dinitro-N--                             propalin  propyl-4-(trifluoromethyl)benzenamide                                methabenz-                                                                               1,3-dimethyl-3-(2-benzothiazolyl)urea                                thiazuron                                                                      metham    methylcarbamodithioic acid                                           methazole 2-(3,4-dichlorophenyl)-4-methyl-1,2,4-                                         oxadiazolidine-3,5-dione                                             methoxuron                                                                               N'--(3-chloro-4-methoxyphenyl)-N,N--                                           dimethylurea                                                         metolachlor                                                                              2-chloro-N--(2-ethyl-6-methylphenyl)-N--                                       (2-methoxy-1-methylethyl)acetamide                                   metribuzin                                                                               4-amino-6-(1,1-dimethylethyl)-3-(methyl-                                       thio)-1,2,4-triazin-5(4H)--one                                       metsulfuron                                                                              2-[[[[(4-methoxy-6-methyl-1,3,5-                                               triazin-2-yl)amino]carbonyl]amino]-                                            sulfonyl]benzoic acid, methyl ester                                  MH        1,2-dihydro-3,6-pyridazinedione                                      molinate  S--ethyl hexahydro-1H--azepine-1-carbo-                                        thioate                                                              monolinuron                                                                              3-( -p-chlorophenyl)-1-methoxy-1-methyl-                                       urea                                                                 monuron   N'--(4-chlorophenyl)-N,N--dimethylurea                               monuron TCA                                                                              salt of monuron and TCA                                              MSMA      monosodium salt of MAA                                               napropamide                                                                              N,N--diethyl-2-(1-naphthalenyloxy)-                                            propanamide                                                          naptalam  2-[(1-naphthalenylamino)carbonyl]-                                             benzoic acid                                                         neburon   1-butyl-3-(3,4-dichlorophenyl)-1-methyl-                                       urea                                                                 nitralin  4-(methylsulfonyl)-2,6-dinitro-N,N--                                           dipropylaniline                                                      nitrofen  2,4-dichloro-1-(4-nitrophenoxy)benzene                               nitrofluorfen                                                                            2-chloro-1-(4-nitrophenoxy)-4-(tri-                                            fluoromethyl)benzene                                                 norea     N,N--dimethyl-N'--(octahydro-4,7-methano-                                      1H--inden-5-yl)urea 3aα,4α,5α,7α,7a.alph               a.-                                                                            isomer                                                               norflurazon                                                                              4-chloro-5-(methylamino)-2-[3-(tri-                                            fluoromethyl)phenyl]-3(2H)--pyridaz-                                           inone                                                                oryzalin  4-(dipropylamino)-3,5-dinitrobenzene-                                          sulfonamide                                                          oxadiazon 3-[2,4-dichloro-5-(1-methylethoxy)-                                            phenyl]-5-(1,1-dimethylethyl)-1,3,4-                                           oxadiazol-2(3H)--one                                                 oxyfluorfen                                                                              2-chloro-1-(3-ethoxy-4-nitrophenoxy)-4-                                        (trifluoromethyl)benzene                                             paraquat  1,1'-dimethyl-4,4'-dipyridinium ion                                  pebulate  S--propyl butylethylcarbamothioate                                   pendimethalin                                                                            N--(1-ethylpropyl)-3,4-dimethyl-2,6-                                           dinitrobenzenamine                                                   perfluidone                                                                              1,1,1-trifluoro-N--[2-methyl-4-(phenyl-                                        sulfonyl)phenyl]methanesulfonamide                                   phenmedipham                                                                             3-[(methoxycarbonyl)amino]phenyl-                                              (3-methylphenyl)carbamate                                            picloram  4-amino-3,5,6-trichloro-2-pyridine-                                            carboxylic acid                                                      PPG-1013  5-(2-chloro-4-(trifluoromethyl)phenoxy)-                                       2-nitroacetophenone oxime-O-acetic                                             acid, methyl ester                                                   procyazine                                                                               2-[[4-chloro-6-(cyclopropylamino)-1,3,5-                                       triazine-2-yl]amino]-2-methylpropane-                                          nitrile                                                              profluralin                                                                              N--(cyclopropylmethyl)-2,6-dinitro-N--                                         propyl-4-(trifluoromethyl)benzen-                                              amine                                                                prometon  6-methoxy-N,N'--bis(1-methylethyl)-                                            1,3,5-triazine-2,4-diamine                                           prometryn N,N'--bis(1-methylethyl)-6-(methyl-                                            thio)-1,3,5-triazine-2,4-diamine                                     pronamide 3,5-dichloro N--(1,1-dimethyl-2-propyn-                                        yl)benzamide                                                         propachlor                                                                               2-chloro-N--(1-methylethyl)-N---phenyl-                                        acetamide                                                            propanil  N--(3,4-dichlorophenyl)propanamide                                   propazine 6-chloro-N,N'--bis(1-methylethyl)-                                             1,3,5-triazine-2,4-diamine                                           propham   1-methylethyl phenylcarbamate                                        prosulfalin                                                                              N--[[4-(dipropylamino)-3,5-dinitro-                                            phenyl]sulfonyl]-S,S--dimethylsulfil-                                          imine                                                                prynachlor                                                                               2-chloro-N--(1-methyl-2-propynyl)acet-                                         anilide                                                              pyrazon   5-amino-3-chloro-2-phenyl-3(2H)--                                              pyridazinone                                                         quizalofop                                                                               (±)-2-[4[(6-chloro-2-quinoxalinyl)]-                              ethyl     oxy]phenoxy]propanoic acid,                                                    ethyl ester                                                          secbumeton                                                                               N--ethyl-6-methoxy-N'--(1-methylpropyl)-                                       1,3,5-triazine-2,4-diamine                                           sethoxydim                                                                               2-[1-(ethoxyimino)butyl]-5-[2-(ethyl-                                          thio)propyl]-3-hydroxy-2-cyclohexene-                                          1-one                                                                siduron   N--(2-methylcyclohexyl)-N'--phenylurea                               simazine  6-chloro-N,N'--diethyl-1,3,5-triazine-                                         2,4-diamine                                                          sulfometuron                                                                             2-[[[[(4,6-dimethyl-2-pyrimidinyl)-                                  methyl    amino]carbonyl]amino]sulfonyl]-                                                benzoic acid, methyl ester                                           TCA       trichloroacetic acid                                                 tebuthiuron                                                                              N--[5-(1,1-dimethylethyl)-1,3,4-thiadi-                                        azol-2-yl]-N,N'--dimethylurea                                        terbacil  5-chloro-3(1,1-dimethylethyl)-6-                                               methyl-2,4(1H,3H)--pyrimidinedione                                   terbuchlor                                                                               N--(butoxymethyl)-2-chloro-N--[2-(1,1-                                         dimethylethyl)-6-methylphenyl]-                                                acetamide                                                            terbuthyl-                                                                               2-(tert-butylamino)-4-chloro-6-(ethyl-                               azine     amino)- .sub.-s-triazine                                             terbutol  2,6-di-tert-butyl- -p-tolyl methylcar-                                         bamate                                                               terbutryn N--(1,1-dimethylethyl)-N'--ethyl-6-                                            methylthio)-1,3,5-triazine-2,4-                                                diamine                                                              thiameturon                                                                              3-[[[[(4-methoxy-6-methyl-1,3,5-                                     methyl    triazin-2-yl)amino]carbonyl]amino]-                                            sulfonyl]2-thiophenecarboxylic acid,                                           methyl ester                                                         thiobencarb                                                                              S--[(4-chlorophenyl)methyl]diethylcar-                                         bamothioate                                                          triallate S--(2,3,3-trichloro-2-propenyl)bis(1-                                          methylethyl)carbamothioate                                           triclopyr [(3,5,6-trichloro-2-pyridinyl)-                                                oxy]acetic acid                                                      tridiphane                                                                               2-(3,5-dichlorophenyl)-2-(2,2,2-                                               trichloroethyl)oxirane                                               trifluralin                                                                              2,6-dinitro-N,N--dipropyl-4-(tri-                                              fluoromethyl)benzenamine                                             trimeturon                                                                               1-( -p-chlorophenyl)-2,3,3-trimethylpseu-                                      dourea                                                               2,4-D     (2,4-dichlorophenoxy)acetic acid                                     2,4-DB    4-(2,4-dichlorophenoxy)butanoic acid                                 vernolate S--propyl dipropylthiocarbamothioate                                 xylachlor 2-chloro-N--(2,3-dimethylphenyl)-N--                                           (1-methylethyl)acetamide                                             ______________________________________                                    

The herbicidal properties of the subject compounds were discovered in a number of greenhouse tests. The test procedures and results follow. ##STR79##

Test A

Seeds of crabgrass (Digitaria spp.), barnyardgrass (Echinochloa crus-galli), giant foxtail (Setaria feberii), wild oats (Avena fatua), cheatgrass (Bromus secalinus), velvetleaf (Abutilon theophrasti), morningglory (Ipomoea spp.), cocklebur (Xanthium pensylvanicum), sorghum, corn, soybean, sugarbeet, cotton, rice, wheat, barley and purple nutsedge (Cyperus rotundus) tubers were planted and treated preemergence with the test chemicals dissolved in a non-phytotoxic solvent. At the same time, these crop and weed species were treated with a soil/foliage application. At the time of treatment, the plants ranged in height from 2 to 18 cm. Treated plants and controls were maintained in a greenhouse for sixteen days, after which all species were compared to controls and visually rated for response to treatment. The ratings, summarized in Table A, are based on a numerical scale extending from 0=no injury, to 10=complete kill. The accompanying descriptive symbols have the following meanings:

C=chlorosis/necrosis;

B=burn;

D=defoliation;

E=emergence inhibition;

G=growth retardation;

H=formative effect;

U=unusual pigmentation;

X=axillary stimulation;

S=albinism; and

Y=abscised buds or flowers.

    TABLE A       CMPD 1 CMPD 2 CMPD 3 CMPD 4 CMPD 5 CMPD 6 CMPD 7 CMPD 8 CMPD 9 CMPD 10      CMPD 11 CMPD 12 CMPD 13 RATE = KG/HA 0.4 0.05 0.4 0.05 0.05 0.05 0.4      0.05 0.4 0.05 0.05 0.01 0.05 0.01 0.4 0.05 0.4 0.05 0.4 0.05 0.4 0.05      0.4 0.05        POSTEMERGENCE COTTON 7B 0 8B 2B 10B 10B 9B 9B 10B 9B 10B 10B 10B 10B      10B 9B 9B 10B 10B 10B 10B 10B 10B 10B MORNINGGLORY 6B 2B 5B 2B 10B 10B      10B 7B 10B 3B 10B 9B 10B 9B 10B 7B 9B 9B 9B 8B 10B 9B 9B 5B COCKLEBUR 4B      0 2B 1B 9B 9B 8B 3B 7B 4B 10B 10B 9B 7B 7B 5B 6B 5B 7B 7B 9B 6B 5B 5B      NUTSEDGE 1B 0 1B 0 10B 8B 9B 0 3B 2B 5B 7B 4B -- 5B 2B 5B 3B 8B 4B 3G 0      5B 1B CRABGRASS 5B 1B 2B 1B 4B 5B 9H 1B 7B 3B 7B 3B 9B 5B 7B 4B 3B 3B 8B      4B 3B,7G 2B 4B 1B BARNYARDGRASS 4B 1B 4B 2B 10B 9B 9B 1B 9B 6B 9B 8B 9B      7B 9B 6B 8B 4B 9B 5B 5B 3B 5B 3B WILD OATS 2B 1B 2B 1B 7B 4B 8B 1B 5B 3B      5B 4B 7B 6B 5B 4B 3B 4B 7B 6B 4B 2B 5B 3B WHEAT 2B 0 1B 1B 5B 4B 8B 0 5B      2B 3B 3B 5B 4B 4B 3B 2B 3B 7B 6B 2B 0 5B 3B CORN 3B 1B 2B 2B 2B 3B 7B 1B      4B 3B 4B 4B 6B 3B 4B 4B 4B 2B 6B 4B 3B 1B 4B 3B SOYBEANS 4B 1B 2C,3G 2B      3B,8G 3B,8G 9B 3B,6G 8B 4B 5B 3B 9B 8B 7B 8B 7B 7B 9B 8B 7B 5B 7B 7B      RICE 4B 1B 1B 1B 5B 7B 8B 2B 6B 5B 5B 4B 7B 6B 5B 4B 4B 4B 9B 5B 4B 2B      6B 4B SORGHUM 3B 1B 1B 1B 9B 5B 8B 3B 5B 4B 4B 3B 6B 6B 5B 5B 4B 4B 9B      4B 4B 3B 3B 2B CHEATGRASS 0 0 1B 1B 3B 1B 1B 0 3B 2B 7B 3B 7B 5B 5B 2B      1B 2B 5B 2B 1B 0 SUGARBEETS 6B 1B 6B 2B 10B 9B 5B,8H 3B,4H 8B 7B 10B 9B      10B 9B 10B 8B 8B 4B 10B 9B 10B 6B 8B 5B VELVETLEAF 7B 2B 7B 3B 10B 10B      10B 9B -- -- 9B 8B 10B 7B 10B 9B 8B 4B 10B 9B -- -- 10B 7B GIANT FOXTAIL      6B 1B 2B 1B 7B 8B 5B 1B 6B 4B 8B 6B 9B 7B 8B 4B 7B 4B 9B 5B 6B 4B 6B 1B      BARLEY 2B 0 2B 1B 2B 2B 2B 0 7B 4B 4B 3B 6B 4B 4B 4B 3B 2B 5B 3B 3B 1B      4B 3B DOWNY BROME                       7B 2B PREEMERGENCE COTTON 0 0 0      0 0 2G 4C,9G 3C 0 0 0 0 3G 0 1H 0 0 0 0 0 0 0 0 0 MORNINGGLORY 0 0 0 0      3C 4C 4C,9G 3C,8G 7G 0 5G 0 10H 2H 10C 0 5G 0 4G 0 2C 0 0 0 COCKLEBUR 0      0 0 0 0 2C 4C,9G 1C 1H 0 2H 0 3H 0 1H 0 0 0 7G 0 0 0 0 0 NUTSEDGE 0 0 0      0 10E 0 9C 0 0 0 0 0 2C 0 0 0 0 0 3G 0 10E 2G 6C 0 CRABGRASS 0 0 0 0 7C      7G 9H 0 6G 0 0 0 9H 8G 9H 3G 6G 0 7G 0 8G 3G 5G 0 BARNYARDGRASS 0 0 0 0      7C 3C,8H 9C 0 3C,6G 0 4C 0 8C 7C 7C 0 2H 0 9C 0 3C,8G 2G 8C 0 WILD OATS      0 0 0 0 0 2G 8C 3C 0 0 0 0 4C 0 4C 0 0 0 7C 0 0 0 2G 0 WHEAT 0 0 0 0 0 0      10C 6C 0 0 0 0 4C 2G 1C 0 0 0 6C 0 0 0 2G 0 CORN 0 0 0 0 0 2C 5C,9H 4C      2C 0 2G 0 4G 0 0 0 0 0 3G 0 0 0 5C 0 SOYBEANS 0 0 0 0 4G 2C 3C,9G 3C,7G      0 0 0 0 4G 0 5G 0 0 0 1C,8G 3G 0 0 2C 0 RICE 0 0 0 0 0 4C 10C 5C 1C 0 0      0 4C 0 1C 0 1C 0 5C 0 0 0 6C 0 SORGHUM 0 0 0 0 6G 2C,5H 10C 6C 1C,4G 0 0      0 9C 0 2G 0 2C 0 9C 0 5G 0 7C 0 CHEATGRASS 0 0 0 0 2G 2G 7C 0 0 0 0 0 0      0 0 0 0 0 0 0 0 0 SUGARBEETS 0 0 0 0 2G 5G 10C 10C 7H 2H 7H 0 8G 3G 7G 0      9G 0 9C 9C 2G 0 5C,9G 3H VELVETLEAF 0 0 0 0 9C 5C 10E 9C 8G 9H 10C 2G      10E 10E 10E 3G 8G -- 10E 6G 9C 3G 10C 0 GIANT FOXTAIL -- 0 0 0 10C 2C,8G      9H 0 9H 0 3H 0 10H 9H 10H 4H 2C,8H 0 8H 0 9G 4G 7H 0 BARLEY 0 0 0 0 0 0      7C 0 1C 0 0 0 2C 0 0 0 0 0 3C 0 0 0 0 0 DOWNY BROME       6G 0        CMPD 14 CMPD 15 CMPD 16 CMPD 17 CMPD 18 CMPD 19 CMPD 20 CMPD 21 CMPD      22 CMPD 23 CMPD 24 CMPD 25 CMPD 26 RATE = KG/HA 0.4 0.05 0.4 0.05 0.4      0.05 0.4 0.05 0.4 0.05 0.4 0.05 0.4 0.05 0.4 0.05 0.4 0.05 0.05 0.05      0.05 0.05        POSTEMERGENCE COTTON 10B 10B 10B 10B 10B 10B 10B 10B 10B 10B 10B 8B      10B 2B 10B 10B 10B 10B 10B 10B 10B 10B MORNINGGLORY 10B 6B 3B 3B 10B 10B      10B 10B 9B 5B 6B 1B 10B 2B 10B 5B 10B 10B 10B 10B 10B 8B COCKLEBUR 7B 5B      4B 3B 8B 6B 9B 6B 7B 3B 1B 1B 6B 2B 7B 4B 10B 9B 10B 10B 10B 7B NUTSEDGE      4B 2B 3B 1B 9B 2B 9B 5B 3B 1B 1B 1B 2B 0 6B 1B 8B 5B -- 4B -- 2B      CRABGRASS 7B 3B 1B 1B 5B 2B 10B 7B 3B 1B 2B 1B 7B 1B 5B 1B 9B 8B 5B 4B      4B 2B BARNYARDGRASS 10B 6B 3B 1B 10B 4B 10B 10B 3B 2B 2B 1B 5B 2B 9B 3B      10B 10B 9B 7B 8B 5B WILD OATS 7B 3B 2B 1B 7B 5B 10B 7B 5B 4B 2B 2B 8B 1B      6B 3B 9B 5B 5B 5B 4B 4B WHEAT 7B 3B 2B 1B 7B 5B 9B 7B 5B 3B 2B 1B 7B 1B      6B 3B 6B 5B 5B 5B 7B 3B CORN 7B 3B 2B 1B 6B 2B 9B 6B 4B 2B 3B 2B 9B 1B      6B 3B 9B 9B 7B 5B 5B 4B SOYBEANS 8B 7B 4B 2B 8B 8B 9B 9B 4B 4B 3B 2B 6B      1B 8B 7B 8B 6B 5B 7B 5B 8B RICE 6B 4B 3B 2B 6B 5B 10B 6B 4B 3B 2B 1B 5B      1B 7B 3B 9B 6B 5B 6B 4B 5B SORGHUM 4B 2B 1B 1B 5B 3B 10B 6B 3B 2B 2B 1B      5B 1B 5B 2B 8B 7B 7B 7B 9B 5B SUGARBEETS 10B 4B 7B 3B 8B 7B 9B 9B 5B 3B      3B 1B 2B 3B 7B 6B 8B 1B 10B 9B 7B 8B VELVETLEAF 10B 6B 7B 2B 10B 9B 10B      10B 10B 5B 7B 2B 5B 2B 10B 8B 10B 10B 10B 9B 10B 10B GIANT FOXTAIL 9B 2B      2B 1B 7B 2B 10B 7B 5B 3B 3B 1B 9B 1B 9B 5B 10B 9B 7B 7B 7B 3B BARLEY 5B      3B 2B 1B 6B 3B 10B 5B 3B 2B 2B 1B 5B 1B 4B 2B 6B 4B 4B 5B 6B 6B DOWNY      BROME 7B 2B 2B 2B 4B 3B 10B 3B 3B 4B 1B 1B 3B 1B 2B 1B 10B 4B 5B 7B 4B      3B PREEMERGENCE COTTON 0 0 0 0 1C 0 10C 2C,7G 0 0 0 0 2G 0 3C,7G 0 0 0      5G 0 0 0 MORNINGGLORY 0 0 0 0 3G 0 10C 2C,8G 0 0 2C 0 0 0 9C 2G 9C 6G 0      0 0 0 COCKLEBUR 0 0 0 0 10G 2G 10C 3C,8G 10C 0 0 0 0 0 2C 0 2G 0 0 0 0 0      NUTSEDGE 8G 0 0 0 2C 0 9C 7C 3C 0 0 0 0 0 8C 0 0 0 0 0 0 0 CRABGRASS 10H      6G 0 0 6G 0 10E 10E 10C 1H 3G 0 2C 0 10H 3C,8H 8G 2G 0 0 0 0 BARNYARDGRAS      S 10H 1H 0 0 8H 2G 10E 10H 7H 4G 0 0 0 0 9H 0 6G 0 0 0 0 0 WILD OATS 7C      0 0 0 4C 0 10C 7C 3G 0 0 0 0 0 7C 3G 0 0 0 0 0 0 WHEAT 3H 0 0 0 2G 0 9C      8C 8C 0 0 0 0 0 3C,7H 0 0 0 0 0 0 0 CORN 2G 0 0 0 1C 0 10H 3C,8H 6C 0 0      0 0 0 7C 0 2G 0 0 0 0 0 SOYBEANS 0 0 0 0 1C 0 10E 9H 2H 0 0 0 0 0 2C,8G      0 2G 2G 0 0 0 0 RICE 0 0 0 0 2G 0 10H 9C 3C,6G 0 0 0 0 0 8C 2C 2C,5G 0 0      0 0 0 SORGHUM 7G 0 0 0 5G 0 10E 10H 10C 0 0 0 1C 0 10C 3C 3C 0 0 0 0 0      SUGARBEETS 6C 0 0 0 9C 3G 10C 10C 7H 1H 0 0 1H 0 9C 7C 8C 3G 5G 0 6C 0      VELVETLEAF 10C 0 0 0 10C 5G 10C 10C 10C 2G 4G 0 2C 0 10C 10C 10C 2C,5G      3G 0 0 0 GIANT FOXTAIL 10H 8H 0 0 9H 2G 10H 10H 10H 8G 7H 0 2G 0 10H 9H      9H 2G 8G 4G 0 8G BARLEY 0 0 0 0 0 0 9C 3C 0 0 0 0 0 0 1C 0 0 0 0 0 0 0      DOWNY BROME 9C 2G 0 0 7G 2G 10C 5G 4G 3G 0 0 2G 0 2C,5G 1C 5G 2G 0 0 0      0   CMPD 27 CMPD 28 CMPD 29 CMPD 30 CMPD 31 CMPD 32 CMPD 33 CMPD 34 CMPD      35 CMPD 36 CMPD 37 RATE = KG/HA 0.1 0.05 0.4 0.05 0.4 0.05 0.4 0.05 0.4      0.05 0.4 0.05 0.4 0.05 0.4 0.05 0.4 0.05 0.4 0.05 0.4 0.05 0.01        POSTEMERGENCE COTTON 10B 10B 10B 10B 10B 10B 10B 10B 10B 10B 10B 10B      10B 10B 10B 10B 10B 10B 10B 10B 10B 10B 10B MORNINGGLORY 10B 10B 10B 10B      10B 10B 10B 10B 10B 10B 10B 10B 10B 10B 10B 10B 10B 10B 10B 10B 10B 10B      9B COCKLEBUR 10B 10B 8B 7B 9B 7B 10B 10B 10B 9B 10B 9B 10B 9B 10B 10B      10B 10B 10B 10B 9B 10B 9B NUTSEDGE -- 2B 7B 6G 10B 8G 9B 9G 5B -- 9B 0      3B 2B 7B 2B 7B 3B 5B 3B 5B 4B 4B CRABGRASS 9B 8B 10B 7B 10B 9B 10B 8B 9B      5B 9B 4B 9B 5B 9B 7B 9B 7B 4B 3B 9B 7B 3B BARNYARDGRASS 10B 10B 10B 4B      10B 10B 10B 9B 9B 7B 9B 7B 8B 5B 9B 4B 9B 6B 4B 3B 10B 7B 3B WILD OATS      6B 5B 10B 4B 10B 5B 9B 4B 7B 3B 6B 3B 6B 3B 7B 3B 7B 4B 4B 3B 7B 5B 2B      WHEAT 7B 5B 9B 5B 10B 8B 8B 4B 5B 3B 7B 5B 6B 3B 6B 3B 7B 4B 4B 3B 4B 3B      1B CORN 5B 5B 10B 3B 9B 4B,7H 4B,8H 4B 5B 3B 8B 3B 6B 4B 7B 3B 7B 4B 4B      3B 5B 3B 2B SOYBEANS 9B 9B 10B 7B 10B 10B 10B 10B 10B 10B 10B9B 10B 9B      9B 9B 10B 10B 6B 8B 10B 6B 5B RICE 7B 5B 9B 4B 10B 9B 9B 5B 7B 5B 7B 5B      6B 4B 7B 4B 7B 5B 5B 4B 7B 4B 4B SORGHUM 6B 5B 8B 4B 10B 9B 9B 7B 9B 7B      9B 5B 8B 4B 7B 3B 9B 5B 5B 7B 5B 3B CHEATGRASS 6B 6B 7B 1B 4B,8H 2B 8B      4B 6B 4B 5B 4B 5B 3B 5B 3B 6B 4B 3B 3B 8B 5B 3B SUGARBEETS 10B 10B 10B      9B 10B 9B 10B 8B 10B 10B 10B 10B 9B 9B 10B 9B 10B 10B 10B 10B 10B 10B 9B      VELVETLEAF 10B 10B 10B 10B 10B 10B 10B 10B 10B 10B 10B 10B 10B 10B 10B      10B 10B 10B 10B 10B 10B 10B 10B GIANT FOXTAIL 9B 9B 10B 8B 10B 9B 10B 9B      10B 6B 9B 6B 8B 7B 10B 5B 9B 7B 6B 3B 10B 6B 3B BARLEY 6B 5B 5B 2B 9B 2B      6B 1B 6B 5B 7B 3B 6B 2B 7B 4B 4B 3B 5B 3B 2B PREEMERGENCE COTTON 4G 0 9H 0       10H 8H 8H 0 7G 2G 2G 0 6H 0 2G 0 5G 2G 2H 0 5G 3H 0 MORNINGGLORY 9H 2H      10H 6H 10H 9H 10H 9H 9H 7H 10E 7G 9H 3H 19H 2G 10E 7H 10H 2H 2H 2H 0      COCKLEBUR 6H 1H 9H 2H 10H 7H 4H -- 10H 2H 9H 0 8H 0 9H 0 9H 1C 1H 0 5H      1H 0 NUTSEDGE 0 0 4C 0 10H 3H 0 0 2C,5G 0 0 0 0 0 0 0 2G --0 0 0 0 0      CRABGRASS 9H 7G 10H 8H 10H 9H 10H 9H 9H 9H 10H 8G 9H 7G 10H 7G 10H 8H 9H      0 10H 7H 7G BARNYARDGRASS 9H 2H 10H 3H 10H 7H 9H 7H 9H 7H 9H 4H 9H 3C,3H      9H 3C,5H 9H 7H 2H 0 8H 1H 0 WILD OATS 5G 0 9H 2H 9H 4H 8H 0 3C,6H 0 7 2H      3C,6H 0 3C,6H 0 3C,7H 0 0 0 3G 0 0 WHEAT 2G 0 9H 0 9H 7H 9H 0 4C,8H 0 9H      2H 3C,7H 0 3C,7H 3C,3G 1H 0 0 3G 0 0 CORN 2G 0 9H 4H 10H 8H 8H 5H 3C,8H      2C,5H 3C,8H 2C,3G 2C,7H 2G 4C,9H 2C,3H 3C,7H 1C,3G 2G 0 2G 0 0 SOYBEANS      0 1H 10H 6G 10H 10H 8H 3H 8H 0 8H 0 9H 4G 8H 3G 7G 1H 3G 0 0 0 0 RICE 0      0 10H 4H 10H 9H 8H 2H 8H 3G 3C,8H 3C,6G 10E -- 3C,8H -- 3C,7G 5G 3G 2G      3G 2G 0 SORGHUM 6G 0 10H 5H 10H 10H 9H 2H 9H 0 2H 0 3G 2G 4H 0 4G 0 2G 0      5G 2G 0 CHEATGRASS 2G 0 7H 0 6H 6H 6H 0 7G 9G 10H 8H 10H 2H 10H 1H 10H      7G 9G 7H 8H 3H 3H SUGARBEETS 3C,8H 2H 10H 9H 10H 10H 10H 7H 10H 1H 10H 0      10H 5H 10H 3H 10H 2G 7H -- 9H 5G 0 VELVETLEAF 10H 7H 10H 10H 10H 10H 10H      10H 10H 6H 10H 5H 9H 4G 10H 5H 10H 4H 9H 0 10H 8H 0 GIANT FOXTAIL 10H 8H      10H 10H 10H 9H 10H 9H 9H 6H 10H 5H 9H 4G 10H 5H 10H 4H 9H 0 10H 8H 0      BARLEY 0 0 8H 0 10H 2H 5H 2H 3C,7H 0 7C 0 7C 1C 7C 1C     0 0 0        CMPD 38 CMPD 39 CMPD 40  CMPD 41 CMPD 42 CMPD 43 CMPD 44 CMPD 45 CMPD      46 CMPD 47 CMPD 48 RATE = KG/HA 0.4 0.05 0.01 0.4 0.05 0.4 0.05 0.4 0.05 0      .4 0.05 0.4 0.05 0.1 0.05 0.05 0.01 0.05 0.01 0.05 0.01 0.05 0.01        POSTEMERGENCE COTTON 10B 10B 10B 10B 10B 10B 10B 10B 10B 10B 10B 10B      10B 9B 9B 10B 10B 10B 10B 10B 10B 10B 10B MORNINGGLORY 10B 10B 9B 10B      10B 10B 10B 10B 10B 10B 10B10B 9B 9B 5B 10B 10B 10B 10B 10B 10B 10B 10B      COCKLEBUR 10B 8B 7B 10B 8B 10B 10B 10B 9B 10B 9B10B 9B 3B 1B 8B 7B 8B 8B      10B 7B 10B 8B NUTSEDGE 10B 9B 4B -- 0 6B 3B 7B 5B 9B -- -- 0 1B 0 3B --      3B -- 3B -- 1B 0 CRABGRASS 10B 10B 7B 10B 8B 8B 7B 10B 6B 10B 8B 9B 7B      2B 1B 4B 2B 4B 2B 6B 3B 6B 3B BARNYARDGRASS 10B 10B 8B 9B 8B 9B 3B 10B      9B 9B 8B 7B 4B 2B 1B 3B 3B 5B 2B 4B 4B 3B 2B WILD OATS 10B 9B 7B 8B 4B      7B 3B 10B 6B 9B 4B 7B 4B 2B 1B 3B 3B 5B 2B 4B 4B 3B 2B WHEAT 10B 8B 6B      8B 4B 5B 2B 7B 6B 8B 5B 7B 4B 1B 1B 2B 2B 4B 3B 2B 1B 4B 1B CORN 10B 9B      7B 8B 6B 5B 3B 6B 4B 8B 6B 5B 4B 3B 1B 3B 2B 4B 3B 3B 2B 3B 2B SOYBEANS      10B 9B 8B 9B 9B 10B 8B 10B 10B 10B 10B 9B 3B 4B 2B 4B 4B 5B 3B 5B 4B 4B      4B RICE 10B 9B 7B 9B 5B 7B 5B 9B 6B 9B 7B 7B 4B 1B 1B 2B 2B 4B 3B 2B 1B      4B 1B SORGHUM 10B 9B 7B 8B 7B 7B 5B 10B 5B 9B 7B 6B 7B 4B 2B 6B 3B 5B 2B      3B 2B 4B 3B CHEATGRASS 10B 9B 4B 6B 4B 5B 3B 8B 5B 7B 5B 5B 3B 1B 1B 5B      1B 3B 0 6B 0 5B 0 SUGARBEETS 10B 10B 9B 10B 8B 10B 9B 10B 10B 10B 9B 10B      10B 4B 2B 10B 6B 10B 6B 10B 2B 10B 6B VELVETLEAF 10B 10B 10B 10B 10B 10B      8B 10B 10B 10B 10B 10B 10B 5B 3B 10B 8B 9B 9B 10B 7B 8B 8B GIANT FOXTAIL      10B 10B 9B 10B 7B 9B 7B 10B 7B 10B 7B 9B 7B 4B 2B 8B 5B 7B 6B 9B 6B 9B      4B BARLEY 10B 8B 6B 7B 6B 5B 3B 7B 4B 8B 6B 5B 5B 2B 2B 2B 2B 1B 1B 2B      1B 1B 1B PREEMERGENCE COTTON 10H 6H 2G 8H 0 3H 0 6H 0 9H 1H 0 0 0 0 0 0      3G 0 0 0 0 0 MORNINGGLORY 10H 9H 2C,8H 9H 7H 7H 2G 5H 4H 10C 10H 9H 0 0      0 9C 0 8G 2G 5C,9H 4H 9H 2H COCKLEBUR 10H 3C,6G 2C 10H 10H 9H 2H 5H 0 7H      2H 6H 0 0 0 0 0 0 0 4H 4H 3H 3H NUTSEDGE 10C -- -- 0 2C,5G 5G 0 3G 0 7G      0 0 10E 0 0 10E 0 3G 0 0 0 10E 0 CRABGRASS 10E 10H 9H 10E 8H 10H 8G 8H      8G 10H 9H 10H 6G 0 0 0 0 0 0 2G 0 2G 0 BARNYARDGRASS 10H 10H 5C,8H 9H 9H      8H 3H 10H 7H 10H 6H 8H 0 0 0 0 0 0 0 0 0 3G 0 WILD OATS 9H 3C,6H 2C      5C,8H 2H 2C,5G 2G 3C,6H 2G 3C,7H 2C,4G 3C,5G 0 0 0 0 0 0 0 0 0 0 0 WHEAT      10H 2C,7H 3C,6G 5C,9H 3C 3C,6G 0 3C,5H 0 9C 3C,6G 3C,6G 0 0 0 0 0 0 0 0      0 0 CORN 10H 4C,9H 3C,8H 4C,9H 3C,6G 3C,7H 3G 2C,5H 0 4C,9H 3C,7H 3C,6H      0 0 0 0 0 0 0 0 0 0 0 SOYBEANS 10E 2C,9G 8G 8G 2G 2H 0 8G 0 9G 4H 3G 0 0      0 0 0 0 0 0 0 0 0 RICE 10H 3C,7G 2C,7G 4C,8G 5G 2C,7G 2G 3G 0 5C,8G      3C,7G 3C,5G 0 0 0 0 0 0 0 0 0 0 0 SORGHUM 10H 9H 8H 9H 7G 3C,7G 0 3C,8H      0 9H 2C,5G 7G 0 0 0 0 0 0 0 0 0 0 0 CHEATGRASS 9H 5G 0 8H 0 4G 2G 4G 2G      3C,7H 2G 5G 0 0 0 0 0 0 0 0 0 0 0 SUGARBEETS 10H 10H 7H 9H 5H 10H 3H 9H      7H 10C 8H 9H 0 0 0 7G 0 4H 0 3H 0 5H 0 VELVETLEAF 10H 10H 10H 10H 9H 10H      9H 10H 9H 10H 10H 10H 5G 0 0 7G 0 8G 4G 9H 3H 5H 2H GIANT FOXTAIL 10H      10H 9H 9H 8H 10H 3H 10H 7H 10H 9H 10H 3G 0 0 0 0 0 0 0 0 2G 0 BARLEY 10H      5C,9H 6C 9C 2C 3C,7H 0 6C 0 8C 2C,6G 3C,7G 0 0 0 0 0 0 0 0 0 0 0        CMPD 49 CMPD 50 CMPD 51 CMPD 52 CMPD 53 CMPD 54 CMPD 55 CMPD 56 CMPD      57 CMPD 58 CMPD 59 CMPD 60 RATE = KG/HA 0.1 0.05 0.01 0.05 0.01 0.05      0.01 0.05 0.01 0.05 0.01 0.05 0.01 0.05 0.01 0.05 0.01 0.05 0.01 0.1      0.05 0.01 0.05 0.01        POSTEMERGENCE COTTON 10B 10B 10B 10B 10B 10B 10B 10B 10B 10B 10B 10B      10B 10B 10B 10B 10B 10B 10B 10B 10B 10B 10B 10B MORNINGGLORY 9B 10B 10B      10B 10B 10B 10B 10B 10B 10B 10B 9B 7B 10B 10B 10B 10B 10B 10B 10B 10B      10B 10B 10B COCKLEBUR 7B 10B 8B 10B 6B 8B 8B 8B 7B 10B 7B 7B 7B 8B 7B      10B 7B 10B 7B 10B 10B 8B 10B 8B NUTSEDGE 1B -- 0 -- 0 3B 0 1B -- 1B --      2B 1B -- 0 -- 2B -- 0 0 0 0 3B 3B CRABGRASS 3B 4B 2B 5B 2B 6B 2B 4B 3B      4B 4B 5B 4B 5B 1B 2B 1B 3B 3B 6B 4B 2B 3B 2B BARNYARDGRASS 8B 9B 8B 9B      3B 9B 4B 10B 4B 9B 6B 10B 5B 10B 5B 8B 3B 8B 2B 9B 8B 5B 4B 2B WILD OATS      3B 2B 1B 3B 2B 3B 2B 2B 1B 2B 2B 4B 2B 5B 3B 5B 3B 2B 3B 5B 4B 3B 2B 2B      WHEAT 2B 2B 1B 2B 1B 2B 1B 1B 1B 3B 2B 4B 1B 3B 2B 2B 2B 1B 1B 3B 2B 1B      2B 1B CORN 3B 4B 1B 2B 2B 2B 2B 3B 1B 2B 4B 2B 1B 6B 2B 2B 2B 3B 2B 5B      3B 1B 2B 1B SOYBEANS 4B 6B 3B 2B 1B 5B 3B 3B 1B 7B 6B 8B 8B 4B 2B 5B 2B      5B 2B 7B 5B 2B 2B,3H 1B RICE 5B 3B 2B 2B 2B 2B 2B 4B 2B 3B 1B 2B 2B 2B      2B 2B 2B 2B 1B 2B 2B 1B 5B 2B SORGHUM 5B 3B 2B 2B 2B 3B 1B 3B 2B 5B 3B      6B 4B 2B 2B 2B 2B 2B 1B 4B 2B 1B 3B 2B CHEATGRASS 2B 2B 2B 2B 1B 5B 1B      1B 0 6B 2B 4B 1B 2B 2B 6B 2B 2B 0 2B 2B 1B 4B 2B SUGARBEETS 4B 10B 6B 9B      5B 10B 5B 9B 5B 10B 4B 9B 8B 10B 7B 9B 6B 10B 2B 8B 10B 6B 10B 6B      VELVETLEAF 7B 10B 10B 6B 6B 10B 7B 4B 6B 10B 7B 10B 9B 9B 5B 10B 8B 10B      6B 10B 10B 7B 10B 6B GIANT FOXTAIL 8B 9B 5B 5B 4B 9B 7B 7B 5B 9B 5B 4B      4B 8B 4B 5B 2B 5B 5B 8B 7B 4B 8B 5B BARLEY 2B 2B 1B 1B 1B 1B 1B 1B 1B 2B      1B 5B 1B 2B 1B 1B 1B 1B 1B 2B 1B 1B 1B 0 PREEMERGENCE COTTON 0 0 0 0 0 0 0       0 0 0 0 2H 0 0 0 0 0 0 0 0 0 0 8H 0 MORNINGGLORY 0 10H 8H 7H 2H 5H 0 7H      3H 10H 3H 2G 0 4C,9H 4H 3H 0 7H 2H 6H 8H 0 8H 0 COCKLEBUR 0 3H 0 0 0 0 0      0 0 2H -- 2G 0 2H 2H 2H 0 0 0 0 0 0 7H 3G NUTSEDGE 0 0 -- 0 0 10E 0 0 0      0 0 0 0 10E 0 0 0 0 -- 10E 10E 0 0 0 CRABGRASS 0 2G 0 0 0 0 -- 0 0 3H 0      3C,8H 3H 0 0 0 0 0 0 3H 0 0 2G 0 BARNYARDGRASS 0 2G 0 0 0 0 0 0 0 0 0      3C,7H 2H 0 0 0 0 0 0 0 0 0 0 0 WILD OATS 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0      0 0 0 0 0 0 0 0 WHEAT 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0      CORN 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 SOYBEANS 0 0 0 0 0      0 0 0 0 0 0 1H 0 0 0 0 0 0 0 0 0 0 0 0 RICE 0 0 0 0 0 0 0 0 0 0 0 0 0 0      0 0 0 0 0 0 0 0 0 0 SORGHUM 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0      0 0 CHEATGRASS 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 SUGARBEETS       0 0 0 3H 3H 3H 3H 0 0 8H 0 3C,8H 5H 8H 0 3H 3H 7H 6H 8H 7H 2H 3C,7H 0      VELVETLEAF 2G 8H 0 0 0 7H 0 8H 0 10H 0 4C,9H 4H 4H 0 7H 0 3H 0 4C,9H 2H      2H 3C,8G 2G GIANT FOXTAIL 2C,6G 4G 0 0 0 4H 2H 0 0 2H 0 4C,9H 4H 0 0 2H      2H 0 0 3H 2H 0 8G 0 BARLEY 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0        CMPD 61 CMPD 62 CMPD 63 CMPD 64 CMPD 65 CMPD 66 CMPD 67 CMPD 68 CMPD      69 CMPD 70 CMPD 71 CMPD 72 RATE = KG/HA 0.05 0.01 0.05 0.01 0.05 0.01      0.4 0.05 0.05 0.01 0.05 0.01 0.05 0.01 0.05 0.01 0.05 0.01 0.4 0.05 0.4      0.05 0.4 0.05        POSTEMERGENCE COTTON 10B 10B 10B 10B 10B 10B 10B 10B 10B 10B 10B 10B      10B 9B 10B 10B 10B 9B 10B 10B 10B 10B 10B 3B MORNINGGLORY 10B 9B 10B 8B      10B 10B10B 10B 10B 10B 10B 8B 7B 8B 10B 9B 10B 10B 10B 10B 10B 10B 10B      10B COCKLEBUR 10B 6B 10B 7B 9B 7B 10B 10B 10B 7B 8B 6B 7B 8B 10B 3B,7H      10B 7B 10B 9B 7B 7B 10B 5B NUTSEDGE -- 1B 1B 0 2B 1B 5B -- 1B 1B 3B 0 5B      0 2B 1B 2B 1B 2B 1B 5B 2B 4B -- CRABGRASS 5B 4B 2B 2B 5B 3B 6B 4B 2B 2B      4B 2B4B 3B 3B 2B 5B 1B 7B 3B 4B 1B 5B 3B BARNYARDGRASS 4B 2B 5B 1B 7B 2B      10B 8B 2B 3B 3B 2B 7B 6B 2B 3B 5B 2B 10B 7B 10B 3B 10B 3B WILD OATS 3B      2B 2B 1B 6B 3B 8B 5B 2B 1B 4B 1B 5B 2B 1B 1B 3B 1B 6B 3B 7B 4B 5B 2B      WHEAT 2B 1B 3B 1B 4B 3B 9B 5B 2B 1B 2B 1B 5B 2B 1B 1B 3B 1B 9B 6B 7B 3B      3B 1B CORN 2B 2B 2B 1B 4B 2B 5B,8H 4B 3B 1B 3B 2B 4B 2B 2B 1B 3B 1B 3B      1B 7B 3B 7B 2B SOYBEANS 3B,6H 2B,2H 1B,1H 1H 7B 3B,6H 10B 10B 3B 0 9B 5B      4B 4B 8B 7B 2B 1B 8B 8B 9B 7B 5B 1B RICE 4B 2B 2B 1B 2B 3B 5B 5B 2B 2B      2B 2B 4B 2B 4B 2B 5B 3B 3B 2B 6B 3B 5B 4B SORGHUM 2B 2B 4B 2B 3B 1B 7B      4B 2B 1B 4B 3B 4B 3B 1B 1B 5B 4B 3B 1B 4B 2B 5B 3B CHEATGRASS 3B 0 1B 0      3B 0 6B 4B 1B 0 2B 0 4B 3B 0 0 5B 1B 1B 0 -- 3B 5B 2B SUGARBEETS 8B 4B      9B 4B 7B 5B 10B 10B 9B 4B 8B 3B 9B 5B 9B 3B,4H 9B 6B 10B 10B 10B 9B 10B      6B VELVETLEAF 10B 3B 9B 3B 6B -- 10B 10B 2B 1B 10B 7B 10B 7B 7B 5B 7B 3B      10B 9B 10B 10B 10B 10B GIANT FOXTAIL 9B 3B 7B 3B 6B 5B 10B 9B 6B 3B 6B      2B 8B 2B 3B 3B 9B 3B 7B 2B 5B 3B -- 1B BARLEY 1B 1B 1B 1B 3B 1B 9B 4B 1B      0 1B 1B 3B 2B 1B 0 3B 1B 7B 5B 6B 3B 5B 2B DOWNY BROME        7B 4B -- -- PREEMERGENCE COTTON 0 0 0 0 0 0 7G 0 0 0  0 0 2H 0 0 0 0 0 2      H 0 2C,9G 0,1C 0 0 MORNINGGLORY 4C,9H 5H 3C,9H 4H 3C,9H 0 10C 3C,8H 0 0      4G 0 4G 0 3C,6H 0 7H 0 9H 9H 2G 0,2G 10C 0 COCKLEBUR 3G 0 0 0 2G 0 3C,7H      0 3G 0 2G 0 0 0 2G 0 2H 0 6H 2H 7G 0,0 5G 0 NUTSEDGE 0 0 0 0 0 0 0 0 0 0      0 0 0 0 0 0 0 0 0 0 7G 0,0 0 0 CRABGRASS 2G 0 0 0 0 0 0 0 0 0 4G 0 4G 0      0 0 2G 0 7H 2H 6G 0,2G 0 0 BARNYARDGRASS 0 0 0 0 0 0 2H 0 0 0 4G 2G 0 0      0 0 2G 0 0 0 10H 5H,4H 3G 0 WILD OATS 0 0 0 0 0 0 2G 2G 0 0 0 0 0 0 0 0      0 0 0 0 6C 0,2G 0 0 WHEAT 0 0 0 0 0 0 3G 0 0 0 0 0 0 0 0 0 0 0 0 0 3C      0,0 0 0 CORN 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 3C 0,0 0 0 SOYBEANS      0 0 0 0 0 0 2G 0 0 0 0 0 0 0 0 0 0 0 0 0 3G 0,0 0 0 RICE 0 0 0 0 0 0 2G      0 0 0 0 0 0 0 0 0 0 0 0 0 4C 0,0 0 0 SORGHUM 0 0 0 0 0 0 2G 0 0 0 0 0 0      0 0 0 0 0 0 0 3C,7G 0,0 0 0 CHEATGRASS 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0      0 0 0 -- 0 0 0 SUGARBEETS 0 0 0 0 0 0 10H 3C,9H 0 0 6H 0 5H 0 0 0 3G 0      10H 4H 10C 5G,5G 8G 0 VELVETLEAF 4C,8G 2G 6G 0 5G 0 10E 5C,9G 0 0 10C 0      4G 0 2C,6H 0 1H 0 10H 8H 10C 5G,0 10C 0 GIANT FOXTAIL 7H 2H 0 0 3G 0 10H      2G 0 0 3C,9H 4G 2G 0 5G 0 0 0 6H 2H 7G 3G,2G 0 0 BARLEY 0 0 0 0 0 0 2G 0      0 0 0 0 0 0 0 0 0 0 0 0 2G 0,0 0 0 DOWNY BROME                     7C 3G      -- --        CMPD 73 CMPD 74 CMPD 75 CMPD 76 CMPD 77 CMPD 78 CMPD 79 CMPD 80 CMPD      81 CMPD 82 CMPD 83 RATE = KG/HA 0.4 0.05 0.4 0.05 0.4 0.05 0.01 0.05      0.01 0.05 0.01 0.4 0.05 0.01 0.4 0.1 0.4 0.05 0.4 0.05 0.4 0.05 0.4      0.05   POSTEMERGENCE COTTON 10B 10B 10B 10B 10B 10B 10B 10B 9B 10B 8B      10B 10B 10B 10B 10B 9B 7B 0 0 9B 2B,8G 10B 9B MORNINGGLORY 10B 10B 10B      8B 10B 10B 8B 10B 8B 9B 5B 10B 10B 9B 10B 10B 8B 7B 0 0 8B 6B 9B 8B      COCKLEBUR 10B 7B 9B 7B 10B 10B 6B 7B 5B 7B 5B 10B 10B 7B 10B 8B 5B 5B 0      0 8B 6B 9B 8B NUTSEDGE 4B -- 5B 1B 3B,9G 9G 2B 4B 1B 3B 1B 4B 1B 0 0 0      3B 1B 0 0 0 0 -- 0 CRABGRASS 6B 1B 4B 2B 10B 9B 3B 3B 1B 2B 1B 6B 2B 1B      5B 2B 4B 1B 0 0 4B 1B 3B 4B BARNYARDGRASS 9B 2B 9B 4B 10B 10B 6B 7B 1B      8B 2B 9B 6B 5B 9B 8B 8B 2B 0 0 5B 2B 4B 4B WILD OATS 6B 3B 4B 3B 10B 5B      3B 5B 2B 4B 3B 6B 2B 1B 3B 3B 7B 2B 0 0 6B 1B 8B 2B WHEAT 5B 1B 3B 4B 6B      3B 3B 5B 2B 4B 2B 6B 1B 1B 4B 2B 5B 1B 0 0 5B 1B 8B 2B CORN 2B 1B 4B 3B      3B 2B 2B 3B 3B 5B 4B 5B 1B 1B 2B 1B 3B 2B 0 0 3B 2B 6B 3B SOYBEANS 7B 4B      8B 7B 10B 9B 7B 8B 3B 7B 4B 8B 2B 3B 7B 3B 8B 5B 0 0 5B 2B,2H 8B 4B RICE      6B 4B 5B 4B 9B 6B 4B 8B 3B 5B 2B 6B 2B 1B 2B 1B 5B 2B 0 0 5B 4B 8B 3B      SORGHUM 9B 5B 5B 4B 10B 5B 3B 3B 2B 5B 2B 8B 5B 5B 4B 1B 4B 3B 0 0 3B 3B      5B 4B CHEATGRASS 6B 1B 5B 1B 8B 5B 3B 3B 1B 5B 2B 6B 1B 0 0 2B 4B 1B 0 0      1B 1B 5B 4B SUGARBEETS 10B 8B 9B 8B 10B 10B 6B 6B 3B 5B 2B 10B 8B 4B 10B      10B 7B 2B 0 0 4H 1B 6B 7B VELVETLEAF 10B 10B 10B 8B 10B 10B 7B 9B 3B 10B      3B 10B 8B 6B 10B 9B 9B 3B 0 0 9B 5B 10B 7B GIANT FOXTAIL 6B 2B 4B 2B 9B      8B 3B 3B 1B 4B 3B 9B 5B 4B 6B 5B 6B 2B 0 0 7B 2B 5B 6B BARLEY 6B 3B 5B      3B 7B 4B 2B 3B 3B 5B 3B 5B 1B 1B 2B 1B 3B 2B 0 0 3B 1B 6B 3B PREEMERGENCE       COTTON 0 0 4G 2G 3H 0 0 2G 0 0 0 10E 8H 0 2C 0 3G 3G 0 0 1C,3H 0 2G 0      MORNINGGLORY 9C 0 3G 0 9H 1H 0 7G 4G 7H 2G 10E 2H 0 10C 3C 7G 3G 0 0 3C      0 8H 0 COCKLEBUR 0 0 5G 2G 2H 0 0 2C,7G 7G 5G -- 8H 0 0 2G 0 7G -- 0 --      0 0 7G 0 NUTSEDGE 0 0 0 -- 10E 0 0 4G 0 3C,5G 0 10E 0 0 0 0 2C,4G 0 0 0      9G 0 3C 0 CRABGRASS 0 0 5G 4G 10H 9H 7G 5G 4G 7G -- 8H 0 0 3C,9G 0 3G 0      0 0 9H 0 8C 0 BARNYARDGRASS 0 0 6H 2G 10H 3H 0 3C,7H 2C,4H 4C,9H 2C,5H      8H 0 0 0 0 9H 7G 0 0 1C 0 7C 0 WILD OATS 0 0 3G 0 8H 0 0 3C,5G 0 7C 2C      3H 0 0 0 0 3C,5G 0 0 0 2C 0 7C 0 WHEAT 0 0 0 0 5H 0 0 3C,6G 0 6C 0 3C,4G      0 0 0 0 3C,6G 0 0 0 0 0 9C 0 CORN 0 0 0 0 3C,7H 1C 0 3C,7G 2C,2H 3C,7H 0      3G 0 0 1C 0 2C,7H 5G 0 0 1C 0 9C 0 SOYBEANS 0 0 0 0 10H 5G 0 2H 7H 6G 0      0 0 0 0 0 2C,5H 0 0 0 2C 0 8C 0 RICE 0 0 0 0 8H 0 0 5G 0 5G 0 6G 0 0 2G      0 6G 0 0 0 3C 0 8C 0 SORGHUM 0 0 0 0 6H 3H 0 3C,5H 0 3C,5H 0 2C,7G 2G 0      2C,5G 0 3C,7H 0 0 0 1C 0 7C 0 CHEATGRASS 0 0 2G 0 4H 2H 0 0 0 4G 0 7G 0      0 0 0 5G 2G 0 0 0 0 7C 0 SUGARBEETS 10C 2G 9C 3G 10H 7H 7G 2C,4G 0 4G 3G      10C 8H 0 9C 4G 3C,8H 0 0 0 2C,8H 0 7H 0 VELVETLEAF 2G 0 8G 9G 10H 10H 5G      10C 4G 4G 0 10C 4H 0 10C 5G 3G -- 0 0 9C 0 10C 0 GIANT FOXTAIL 0 0 6G 2G      10H 10H 3G 10E 3G 5G 0 7H 3G 0 8G 0 9H 5G 0 0 4C,9H 0 10C 0 BARLEY 0 0 0      0 2H 0 0 8C 1C 7C 0 4G 0 0 0 0 5C 0 0 0 0 0 7C 0        RATE = KG/HA 0.4 0.05 0.4 0.05 0.4 0.05 0.4 0.05 0.4 0.05 0.4 0.05 0.4 0      .05 0.4 0.05 0.05 0.4 0.05 0.4 0.05 0.4 0.05        POSTEMERGENCE COTTON 10B 9B 10B 8B 10B 10B 7B 0 1B 0 3C 0 1B 0 9B 8B      10B 10B 10B 2B 0 10B 9B MORNINGGLORY 3B 1B 7B 3B 8B 7B 3B 0 1B 0 2C,2H      1C,1H 1B 0 8B 5B 10B 10B 9B 1B 0 9B 9B COCKLEBUR 2B 0 5B 3B 4B 1B 2B 0 0      0 0 0 0 0 4B 4B 4B 10B 8B 0 0 7B 4B NUTSEDGE 0 0 2B -- 2B 1B 0 -- -- 0      2G 0 0 0 3B 1B 2B 3B,8G 0 0 0 -- 2B CRABGRASS 1B 1B 5B 2B 2B 1B 1B 0 0 0      0 0 0 0 3B 1B 2B 10B 9B 0 0 9B 4B BARNYARDGRASS 2B 1B 6B 2B 4B 2B 4B 0      1B 0 0 0 0 0 6B 2B 3B 10B 7B 0 0 9B 6B WILD OATS 1B 0 2B 1B 3B 2B 0 0 0      0 0 0 0 0 3B 2B 2B 5B 2B 0 0 5B,9H 3B WHEAT 0 0 2B 1B 3B 2B 0 0 0 0 0 0      0 0 3B 2B 2B 4B 1B 0 0 6B,9H 4B CORN 1B 1B 4B 3B 3B 2B 2B 0 0 0 1C 0 0 0      3B 3B 2B 3B 1B 0 0 9B 5B SOYBEANS 3B 2B 6B 2B 7B 3B 1B 0 0 0 0 0 2B 0 7B      5B 5B 9B 5B 0 0 9B 9B RICE 2B 0 5B 4B 5B 2B 1B 0 0 0 0 0 0 0 5B 3B 4B 8B      1B 0 0 8B 6B SORGHUM 3B 1B 3B 3B 4B 3B 4G 0 0 0 0 0 0 0 5B 2B 2B 6B 3B 0      0 9B 5B CHEATGRASS 2B 0 1B 0 3B 1B 0 0 0 0 0 0 0 0 5B 2B -- 3B 1B 0 0 2B      1B SUGARBEETS 3B,5H 0 8B 3B 5B 2B 3B 0 0 0 1C 0 1B 0 6B 5B 5B 10B 9B 0 0      9B 7B VELVETLEAF 6B 3B 10B 7B 9B 7B 1B 0 0 0 6G 0 0 0 7B 7B 7B 10B 10B 0      0 10B 10B GIANT FOXTAIL 3B 1B 3B 1B 4B 1B 2B 0 0 0 0 0 0 0 6B 2B 3B 9B      4B 0 0 9B 4B BARLEY 1B 1B 2B 1B 3B 2B 0 0 0 0 0 0 0 0 2B 2B 2B 2B 0 0 0      5B 3B DOWNY BROME               -- -- 4B PREEMERGENCE COTTON 0 0 0 0 0 0 0       0 0 0 0 0 0 0 3C,5G 2G 0 1H 0 0 0 9C 2C,5G MORNINGGLORY 0 0 0 0 0 0 0 0      0 0 0 0 0 0 2C,7G 0 2G 6H 0 0 0 10C 9C COCKLEBUR 0 0 0 0 0 0 0 0 0 0 0 0      0 0 -- 0 0 9H 0 0 0 9C 2C,5G NUTSEDGE 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0      0 0 0 0 9C 0 CRABGRASS 0 0 7H 0 6G 0 0 0 0 0 0 0 4G 0 3C,9H 5G 0 10H 7H      0 0 10H 10H BARNYARDGRASS 0 0 1H 0 1H 0 0 0 0 0 0 0 0 0 8C 2G 0 8H 0 0 0      9H 1C WILD OATS 0 0 0 0 0 0 0 0 0 0 0 0 0 0 3C,6G 4G 0 2H 0 0 0 3C,8H      2C,5H WHEAT 0 0 0 0 0 0 0 0 0 0 0 0 0 0 4C,8H 2G 0 0 0 0 0 5C,9H 1C CORN      0 0 0 0 0 0 0 0 0 0 0 0 0 0 5C,9H 2C 0 1H 0 0 0 9C 3C,6G SOYBEANS 0 0 0      0 0 0 0 0 0 0 0 0 0 0 3C,7G 0 2G 3H 0 0 0 5C,9H 3C,9G RICE 0 0 0 0 0 0 0      0 0 0 0 0 0 0 7C 0 0 3H 0 0 0 9H 4C,6G SORGHUM 0 0 0 0 0 0 0 0 0 0 0 0 0      0 9C 2C 0 6H 0 0 0 9H 3C,5G CHEATGRASS 0 0 0 0 0 0 0 0 0 0 0 0 0 0 3G 2G      -- 0 0 0 0 3C 0 SUGARBEETS 0 0 0 0 2G 0 0 0 0 0 0 0 0 0 3C,8G 8G 0 10H      2H 0 0 10C 9C VELVETLEAF 2H 0 0 0 2H 0 0 0 0 0 0 0 2G 0 10C 2G 0 10H 3H      0 0 10C 10C GIANT FOXTAIL 0 0 2G 0 2H 0 0 0 0 0 0 0 0 0 10H 6G 0 10H 4H      0 0 10H 9H BARLEY 0 0 0 0 0 0 0 0 0 0 0 0 0 0 8C 0 0 0 0 0 0 4C 0 DOWNY      BROME               -- -- 0        CMPD 96 CMPD 97 CMPD 98 CMPD 99 CMPD 100 CMPD 101 RATE = KG/HA 0.4      0.05 0.05 0.05 0.05 0.05 0.05        POSTEMERGENCE COTTON 9B 9B 10B 10B 10B 9B 10B MORNINGGLORY 7B 3B 10B      10B 10B 10B 10B COCKLEBUR 5B 4B 9B 7B 8B 9B 9B NUTSEDGE 2B 0B 5B 5B --      3B 5B CRABGRASS 4B 2B 5B 3B 4B 5B 4B BARNYARDGRASS 3B 1B 9B 7B 7B 9B 5B      WILD OATS 3B 2B 5B 5B 5B 2B 2B WHEAT 1B 0 5B 4B 4B 2B 1B CORN 2B 1B 3B      5B 5B 4B 4B SOYBEANS 6B 3B 7B 6B 9B 5B 6B RICE 2B 1B 6B 3B 5B 4B 2B      SORGHUM 4B 2B 4B 5B 5B 5B 8B CHEATGRASS 1B 0 -- 3B 4B 2B 2B SUGARBEETS      5B 2B 5B 9B 10B 10B 10B VELVETLEAF 2B -- 10B 10B 10B 9B 10B GIANT      FOXTAIL 2B 1B 7B 5B 7B 9B 4B BARLEY 1B 1B 3B 3B 6B 3B 1B DOWNY BROME      6B -- PREEMERGENCE COTTON 0 0 0 0 0 0 0 MORNINGGLORY 4G 0 0 0 0 0 2G      COCKLEBUR -- 0 3G 0 0 0 0 NUTSEDGE 0 0 2C 0 0 0 0 CRABGRASS 3H 0 3C,8G      2G 0 0 0 BARNYARDGRASS 0 0 0 0 3G 0 0 WILD OATS 0 0 0 0 0 0 0 WHEAT 0 0      0 0 0 0 0 CORN 0 0 0 0 0 0 0 SOYBEANS 0 0 0 0 0 0 0 RICE 0 0 3C 0 0 0 0      SORGHUM0 0 2C 0 0 0 0 CHEATGRASS 0 0 -- 0 0 0 0 SUGARBEETS 0 0 0 0 2G 5G      0 VELVETLEAF 0 0 2G 5G 0 5G 4G GIANT FOXTAIL 2H 0 3C,6G 2G 0 0 0 BARLEY      0 0 0 0 0 0 0 DOWNY BROME   0 --

It is noted that several compounds of this test show little or no activity; it is thought that greater activity would be shown at higher rates of use.

In the following examples, the species of plants that were tested were:

    ______________________________________                                                              Abbreviation                                              ______________________________________                                         Barnyardgrass (watergrass)-                                                                           BYGR                                                    Echinochloa crus-galli                                                         Downy brome - Bromus tectorum                                                                         DOBR                                                    Yellow foxtail - Setaria glauca                                                                       YEFT                                                    Sicklepod - Cassia obtusifolia                                                                        SIPO                                                    Velvetleaf - Abutilon theophrasti                                                                     VELE                                                    Garden cress - Lepidium sativum                                                                       GACR                                                    Johnsongrass - Sorghum halepense                                                                      JOGR                                                    Morningglory - Ipomoea sp.                                                                            MOGL                                                    Field bindweed - Convolvulus arvensis                                                                 FIBW                                                    Nightshade - Solanum sp.                                                                              NISH                                                    Blackgrass - Alopercursus myosurides                                                                  BLGR                                                    Yellow millet - Panicum miliceum                                                                      YEMI                                                    Large crabgrass - Digitaria sanguinalis                                                               LACG                                                    Redroot pigweed - Amaranthus retroflexus                                                              RRPW                                                    Hemp sesbania - Sesbania exaltata                                                                     HESE                                                    Prickly sida - Sida spinosa                                                                           PRSI                                                    ______________________________________                                    

Test Procedures

The preemergence (soil) herbicidal activity of compounds of formula I were evaluated by planting seeds of downy brome, johnsongrass, yellow foxtail, barnyardgrass, yellow millet, blackgrass, hemp sesbania, velvetleaf, morningglory, prickly sida, sicklepod and garden cress in test tubes, nominally measuring 25×200 millimeters, filled about three-quarters full of untreated soil, in each case covered on top with about 2.5 cubic centimeters of soil, treated with 0.1 milligram of the test compound, to give a dosage of 1.0 pound of test compound per acre. The seeds were planted on top of the treated soil and covered with about 1.5 cubic centimeters of untreated soil. The planted soil was held under a controlled regiment of temperature, moisture, and light. At 10 days, the amounts of germination and growth in each tube were evaluated on a 0 to 9 scale.

The postemergence (foliar) herbicidal activity of compounds of formula I were evaluated by spraying 9-day-old large crabgrass plants, 9-day-old pigweed plants, 6-day-old johnsongrass plants, 9-day-old velvetleaf plants, 8-day-old yellow foxtail plants, 9-day-old sicklepod plants, 5-day-old morningglory plants, 5-day-old barnyardgrass plants, 6-day-old yellow millet plants, 9-day-old nightshade plants, 9-day-old prickly sida plants and 7-day-old field bindweed plants to runoff with 2.4 milliliters of a liquid formulation containing 0.5 milligram of the test compound (one pound of the test compound per acre). The sprayed plants were held under a controlled regiment of temperature, moisture and light for 7 to 8 days, when the effect of the test compound was evaluated visually.

Results of the preemergence and postemergence herbicidal activity tests are set forth in Tables 1 and 22.

                  TABLE A-1                                                        ______________________________________                                         Preemergence                                                                   CMPD                                                                           NO.   DOBR     JOGR    YEFT   BYGR  YEMI   BLGR                                ______________________________________                                         102   0        6       3      7     5      0                                   103   6        7       4      7     7      7                                   104   0        3       0      4     0      4                                   105   7        7       6      8     7      6                                   106   0        5       3      3     0      3                                   107   3        3       4      4     3      3                                   108   0        0       0      0     0      0                                   109   5        6       6      6     6      5                                   110   5        4       5      6     6      3                                   111   0        0       0      0     0      0                                   112   0        0       0      0     0      0                                   113   0        0       0      0     0      0                                   114   3        0       4      4     3      0                                   115   3        0       0      5     0      3                                   116   0        0       0      0     0      0                                   117   7        5       5      7     8      3                                   118   0        0       0      0     0      0                                   ______________________________________                                         CMPD                                                                           NO.   HESE     VELE    MOGL   PRSI  SIPO   GACR                                ______________________________________                                         102   0        0       0      6     0      5                                   103   8        8       8      9     3      9                                   104   5        7       0      8     0      6                                   105   8        9       9      9     7      9                                   106   3        9       8      9     0      9                                   107   3        9       7      9     0      9                                   108   --       3       0      3     0      9                                   109   8        6       6      8     3      9                                   110   7        7       3      8     0      9                                   111   0        3       5      8     0      8                                   112   0        0       0      0     0      0                                   113   2        5       4      8     2      9                                   114   3        9       9      9     3      9                                   115   3        7       5      9     0      9                                   116   0        4       7      3     0      6                                   117   9        9       9      9     0      9                                   118   0        0       0      0     0      0                                   ______________________________________                                         Postemergence                                                                  CMPD                                                                           NO.   DOBR     JOGR    YEFT   BYGR  YEMI   BLGR                                ______________________________________                                         102   3        3       3      3     5      7                                   103   5        9       9      8     8      9                                   104   7        9       9      9     9      9                                   105   7        6       9      6     7      9                                   106   3        2       2      3     3      6                                   107   8        9       9      9     8      9                                   108   2        7       7      7     7      6                                   109   3        5       5      3     3      7                                   110   3        4       5      3     3      5                                   111   6        5       8      7     6      9                                   112   5        3       4      3     4      5                                   113   8        9       9      8     8      9                                   114   6        9       9      6     7      9                                   115   8        9       9      9     9      9                                   116   4        7       6      3     5      9                                   117   9        5       9      9     8      9                                   118   3        4       3      3     5      3                                   ______________________________________                                         CMPD                                                                           NO.   HESE     VELE    MOGL   PRSI  SIPO   GACR                                ______________________________________                                         102   9        7       8      6     3      9                                   103   9        9       9      9     8      9                                   104   9        9       9      9     8      9                                   105   9        9       9      9     9      9                                   106   7        3       9      6     4      9                                   107   9        9       9      9     3      9                                   108   8        7       9      8     7      7                                   109   9        5       9      6     0      9                                   110   9        3       8      7     3      9                                   111   9        8       9      9     5      0                                   112   9        5       6      6     4      5                                   113   9        9       9      9     4      9                                   114   9        9       9      9     8      9                                   115   9        9       9      9     9      9                                   116   9        6       9      8     4      9                                   117   9        9       9      9     7      9                                   118   9        4       8      5     3      5                                   ______________________________________                                    

Test B

Postemergence

Three round pans (25 cm diameter by 12.5 cm deep) were filled with Sassafras sandy loam soil. One pan was planted with nutsedge (Cyperus rotundus) tubers, crabgrass (Digitaria sanguinalis), sicklepod (Cassia obtusifolia), jimsonweed (Datura stramonium), velvetleaf (Abutilon theophrasti), lambsquarters (Chenopodium album), rice (Oryza sativa), and teaweed (Sida spinosa). The second pot was planted with green foxtail (Setaria viridis), cocklebur (Xanthium pensylvanicum), morningglory (Ipomoea hederacea), cotton (Gossypium hirsutum), johnsongrass (Sorghum halepense), barnyardgrass (Echinochloa crus-galli), corn (Zea mays), soybean (Glycine max), and giant foxtail (Setaria faberi). The third pot was planted with wheat (Triticum aestivum), barley (Hordeum vulgare), wild buckwheat (Polygonum convolvulus L.), downy brome (Bromus tectorum L.), sugarbeet (Beta vulgaris), wild oat (Avena fatua L.), common chickweed (Stellaria media), blackgrass (Alopecurus myosuroides), and rape (Brassica napus). The plants were grown for approximately fourteen days, then sprayed postemergence with the chemicals dissolved in a non-phytotoxic solvent.

Preemergence

Three round pans (25 cm diameter by 12.5 cm deep) were filled with Sassafras sandy loam soil. One pan was planted with nutsedge tubers, crabgrass, sicklepod, jimsonweed, velvetleaf, lambsquarters, rice and teaweed. The second pot was planted with green foxtail, cocklebur, morningglory, cotton, johnsongrass, barnyardgrass, corn, soybean, and giant foxtail. The third port was planted with wheat, barley, wild buckwheat, downy brome, sugarbeet, wild oat, chickweed, blackgrass, and rape. The three pans were sprayed preemergence with the chemicals dissolved in a non-phytotoxic solvent.

Treated plants and controls were maintained in the greenhouse for approximately 24 days, then all rated plants were compared to controls and visually reated for plant response.

Response ratings are based on a scale of 0 to 100 where 0=no effect, and 100=complete control. A das (-) response means no test.

Response ratings are contained in Table B

                  TABLE B                                                          ______________________________________                                         CMPD 17                                                                        RATE = G/HA   0500     0250     0062   0016                                    ______________________________________                                         POSTEMERGENCE                                                                  GIANT FOXTAIL 100      100      100    40                                      VELVETLEAF    100      100      100    100                                     SUGARBEETS    100      100      100    100                                     CRABGRASS     100      100      100    40                                      TEAWEED       100      100      100    100                                     JIMSONWEED    100      100      100    80                                      RICE          100      100      30     20                                      COCKLEBUR     100      70       60     40                                      COTTON        100      100      100    100                                     SOYBEANS      100      90       80     70                                      BARNYARDGRASS 100      100      100    20                                      WILD OATS     100      90       30     20                                      MORNINGGLORY  100      100      100    40                                      WHEAT         40       --       10     0                                       SICKLEPOD     100      90       80     50                                      JOHNSONGRASS  100      100      100    30                                      NUTSEDGE      100      80       50     30                                      CORN          90       80       10     0                                       WILD BUCKWHEAT                                                                               100      100      100    100                                     BLACKGRASS    100      100      90     40                                      RAPE          100      100      100    60                                      BARLEY        100      20       10     0                                       GREEN FOXTAIL 100      100      100    100                                     LAMBSQUARTER  100      100      100    100                                     CHICKWEED     100      100      --     100                                     DOWNY BROME   100      100      30     0                                       PREEMERGENCE                                                                   GIANT FOXTAIL 100      100      100    100                                     VELVETLEAF    100      100      100    90                                      SUGARBEETS    100      100      100    70                                      CRABGRASS     100      100      100    100                                     TEAWEED       100      100      100    80                                      JIMSONWEED    100      100      100    40                                      RICE          100      100      100    90                                      COCKLEBUR     90       85       70     50                                      COTTON        100      100      60     20                                      SOYBEANS      100      100      70     30                                      BARNYARDGRASS 100      100      100    90                                      WILD OATS     100      80       50     20                                      MORNINGGLORY  100      100      80     40                                      WHEAT         100      60       20     10                                      SICKLEPOD     100      100      90     50                                      JOHNSONGRASS  100      100      100    90                                      NUTSEDGE      100      100      60     20                                      CORN          100      100      100    50                                      WILD BUCKWHEAT                                                                               100      100      100    100                                     BLACKGRASS    100      100      100    40                                      RAPE          100      100      90     40                                      BARLEY        100      70       50     20                                      GREEN FOXTAIL 100      100      100    100                                     LAMBSQUARTER  100      100      100    100                                     CHICKWEED     60       50       30     20                                      DOWNY BROME   100      100      90     40                                      ______________________________________                                         CMPD 42                                                                        RATE = G/HA   0250     0062     0016   0004                                    ______________________________________                                         POSTEMERGENCE                                                                  GIANT FOXTAIL 100      70       30     0                                       VELVETLEAF    100      100      100    30                                      SUGARBEETS    100      70       90     50                                      CRABGRASS     100      50       0      0                                       TEAWEED       100      100      70     20                                      JIMSONWEED    100      100      100    30                                      RICE          100      70       40     20                                      COCKLEBUR     80       70       80     20                                      COTTON        100      100      100    20                                      SOYBEANS      70       50       70     20                                      BARNYARDGRASS 100      90       40     0                                       WILD OATS     100      40       20     0                                       MORNINGGLORY  100      100      100    0                                       WHEAT         50       20       20     0                                       SICKLEPOD     100      80       40     0                                       JOHNSONGRASS  100      70       30     30                                      NUTSEDGE      50       40       20     0                                       CORN          30       40       20     0                                       WILD BUCKWHEAT                                                                               100      100      100    30                                      BLACKGRASS    50       30       0      0                                       RAPE          100      100      100    0                                       BARLEY        80       20       20     0                                       GREEN FOXTAIL 100      90       50     0                                       LAMBSQUARTER  100      100      100    90                                      CHICKWEED     90       40       70     40                                      DOWNY BROME   30       10       30     0                                       ______________________________________                                         CMPD 42                                                                        RATE = G/HA   0500     0250     0062   0016                                    ______________________________________                                         PREEMERGENCE                                                                   GIANT FOXTAIL 100      100      90     70                                      VELVETLEAF    100      100      100    100                                     SUGARBEETS    100      100      30     50                                      CRABGRASS     100      100      100    90                                      TEAWEED       100      100      70     80                                      JIMSONWEED    100      100      100    80                                      RICE          90       90       40     20                                      COCKLEBUR     100      100      20     60                                      COTTON        100      80       40     0                                       SOYBEANS      60       80       10     0                                       BARNYARDGRASS 100      100      100    70                                      WILD OATS     100      100      70     30                                      MORNINGGLORY  100      100      70     0                                       WHEAT         90       40       0      0                                       SICKLEPOD     100      100      90     0                                       JOHNSONGRASS  100      100      90     20                                      NUTSEDGE      60       30       0      20                                      CORN          90       80       70     20                                      WILD BUCKWHEAT                                                                               100      100      100    70                                      BLACKGRASS    80       70       50     20                                      RAPE          100      100      --     80                                      BARLEY        70       30       0      0                                       GREEN FOXTAIL 100      100      100    100                                     LAMBSQUARTER  100      100      100    100                                     CHICKWEED     60       60       0      0                                       DOWNY BROME   80       90       60     0                                       ______________________________________                                         CMPD 78                                                                        RATE = G/HA   0250   0062    0016  0004  0001                                  ______________________________________                                         POSTEMERGENCE                                                                  GIANT FOXTAIL 0      0       0     0     0                                     VELVETLEAF    100    90      70    50    0                                     SUGARBEETS    100    100     100   50    90                                    CRABGRASS     0      0       0     0     0                                     TEAWEED       100    80      60    50    0                                     JIMSONWEED    100    100     70    30    40                                    RICE          0      0       0     0     0                                     COCKLEBUR     40     30      0     0     0                                     COTTON        90     80      40    30    30                                    SOYBEANS      0      0       0     0     0                                     BARNYARDGRASS 30     0       0     0     0                                     WILD OATS     0      0       0     0     0                                     MORNINGGLORY  80     50      40    30    50                                    WHEAT         0      0       0     0     0                                     SICKLEPOD     0      0       0     0     0                                     JOHNSONGRASS  0      0       0     0     0                                     NUTSEDGE      0      0       0     0     0                                     CORN          0      0       0     0     0                                     WILD          100    100     60    0     30                                    BUCKWHEAT                                                                      BLACKGRASS    30     0       0     0     0                                     RAPE          100    60      30    0     0                                     BARLEY        0      0       0     0     0                                     GREEN FOXTAIL 0      0       0     0     0                                     CHEATGRASS    --     50      30    0     0                                     LAMBSQUARTER  100    100     70    50    0                                     CHICKWEED     50     30      0     0     0                                     DOWNY BROME   0      0       0     0     --                                    ______________________________________                                         CMPD 78                                                                        RATE = G/HA   0500     0250     0062   0016                                    ______________________________________                                         PREEMERGENCE                                                                   GIANT FOXTAIL 100      70       30     0                                       VELVETLEAF    100      100      70     30                                      SUGARBEETS    100      100      80     40                                      CRABGRASS     100      90       80     70                                      TEAWEED       100      100      70     50                                      JIMSONWEED    90       70       0      0                                       RICE          0        0        0      0                                       COCKLEBUR     70       50       30     0                                       COTTON        60       30       0      0                                       SOYBEANS      20       0        0      0                                       BARNYARDGRASS 50       30       0      0                                       WILD OATS     30       0        0      0                                       MORNINGGLORY  100      100      90     70                                      WHEAT         0        0        0      0                                       SICKLEPOD     60       30       0      0                                       JOHNSONGRASS  70       60       50     30                                      NUTSEDGE      0        0        0      0                                       CORN          0        0        0      0                                       WILD BUCKWHEAT                                                                               100      90       60     30                                      BLACKGRASS    50       30       0      0                                       RAPE          90       50       0      0                                       BARLEY        0        0        0      0                                       GREEN FOXTAIL 100      70       30     0                                       CHEATGRASS    --       0        0      0                                       LAMBSQUARTER  100      100      90     70                                      CHICKWEED     30       0        0      0                                       DOWNY BROME   30       0        0      0                                       ______________________________________                                    

Test C

Seeds of the treated crop and weed species were planted in a blend of peat and sandy loam and grown in the greenhouse for 10 to 21 days before postemergence treatment of the subject herbicide. Preemergence treatments were prepared immediately before herbicide application using sandy loam soil as the planting media. The compound of interest was diluted in a non-phytotoxic solvent composed of; acetone, water, a humectant and Poe sorbitan monolaurate, with aliquots taken for the various rates tested. Herbicide applications were made using a belt spray applying the material over the plant leaves for postemergence treatments and over the moistened soil surface in the preemergence treatments. After herbicide treatment, the pots were removed to the greenhouse where they were maintained under standard conditions for 21 days at which time visual evaluations of each species were made using a scale of 0 equal to no injury or control and 100 equal to complete kill of the plant. The data for this evaluation is shown in Table C.

                  TABLE C                                                          ______________________________________                                         CMPD 17                                                                        RATE G/HA      0250    0125    0064  0032 0016                                 ______________________________________                                         POSTEMERGENCE                                                                  ERA WHEAT      0       0       0     0    0                                    KLAGES BARLEY  30      10      10    10   10                                   WILD OATS      90      60      20    10   0                                    DOWNY BROME    10      10      0     0    0                                    CHEAT GRASS    10      10      0     0    0                                    BLACKGRASS     50      20      10    10   10                                   ANN. BLUEGRASS 60      10      10    10   0                                    GREEN FOXTAIL  100     100     100   100  100                                  ITALN. RYEGRASS                                                                               90      70      30    10   10                                   ALTEX RAPE     100     70      50    20   20                                   CENTURK WHEAT  20      0       0     0    0                                    IGRI BARLEY    30      10      10    10   10                                   JOINT GOATGRASS                                                                               10      10      10    0    0                                    WILD OATS STG 2                                                                               0       0       0     0    0                                    BLACKGRASS STG 2                                                                              40      10      10    0    0                                    CTCHWD BEDSTRAW                                                                               90      50      40    20   10                                   WILD BUCKWHEAT 100     100     100   100  60                                   KOCHIA         100     100     100   70   60                                   SNTLS CHAMOMILE                                                                               100     70      10    0    0                                    BLACK NIGHTSHADE                                                                              100     100     100   100  80                                   PERSN SPEEDWELL                                                                               100     100     70    70   60                                   USH11 SUGARBEET                                                                               100     90      90    70   70                                   IVYLF SPEEDWELL                                                                               100     100     100   30   0                                    LAMBSQUARTER   100     100     90    80   60                                   FIELD PENNYCRES                                                                               100     70      70    30   30                                   FIELD VIOLET   100     100     90    70   70                                   PREEMERGENCE                                                                   ERA WHEAT      100     100     90    70   70                                   KLAGES BARLEY  90      70      70    50   40                                   WILD OATS      100     90      90    70   60                                   DOWNY BROME    60      60      20    0    0                                    CHEAT GRASS    100     90      70    70   60                                   BLACKGRASS     100     80      60    60   40                                   ANN. BLUEGRASS 100     100     100   80   70                                   GREEN FOXTAIL  100     100     100   100  100                                  ITALN. RYEGRASS                                                                               100     100     100   80   70                                   ALTEX RAPE     100     90      90    70   70                                   CENTURK WHEAT  100     100     80    70   70                                   IGRI BARLEY    90      90      70    50   40                                   JOINT GOATGRASS                                                                               70      40      40    40   30                                   CTCHWD BEDSTRAW                                                                               80      60      60    20   20                                   WILD BUCKWHEAT 100     100     100   100  70                                   KOCHIA         100     100     100   100  70                                   SNTLS CHAMOMILE                                                                               100     100     100   100  100                                  BLACK NIGHTSHAD                                                                               100     100     100   100  100                                  PERSN SPEEDWELL                                                                               100     70      70    60   40                                   USH11 SUGARBEET                                                                               100     100     100   100  100                                  IVYLF SPEEDWELL                                                                               100     100     100   100  80                                   LAMBSQUARTER   100     100     100   100  100                                  FIELD PENNYCRES                                                                               100     100     100   100  100                                  FIELD VIOLET   100     90      90    90   70                                   ______________________________________                                     

What is claimed is:
 1. A compound of the formula ##STR80## wherein, R is H, Cl, F, C₁ -C₂ alkyl or C₁ -C₃ alkoxy;R₁ is H, F, Cl, Br, CH₃, OCH₃, CN, CF₃, OCF₃ or OCF₂ H; X¹ is O R₂ is H, CH₃ or CH₂ CH₃ ; R₃ is H, C₁ -C₄ haloalkyl, CR₂ R₇ CN, CN, CR₂ R₄ R₇, COCl, COR₄, C(NOR₆)R₂, CO₂ R₄, CONR₄ R₂, CHR₂ OH, CO₂ (CH₂)₂ SI(CH₃)₃, CONR₂ SO₂ CH₃, CHR₂ CO₂ R₄, CONHCH(CH₃)CONHCH(CH₃)CO₂ CH₃, CHR₂ COR₄, CHR₂ OSO₂ (C₁ -C₄ alkyl), CHR₂ OC(O)R₄, CHR₂ OC(O)N(R₂)₂, CHR₂ OC(O)N(R₂)OCH₃, CHR₂ OC(O)N(R₂)Ph, HC═CH₂ or C.tbd.CH; R₄ is H, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₂ -C₆ alkenyl, C₃ -C₆ alkynyl, C₂ -C₄ haloalkenyl, phenyl, C₁ -C₄ alkylphenyl, C₃ -C₆ alkoxycarbonylalkyl or (CH₂ CH₂ O)_(b) R₂ ; b is 1 to 6; m is 1; n is 1 or 2 J is ##STR81## wherein X and Y each is O or S; Z is C or N; W is S or SO₂ ; R₆ is H, C₁ -C₅ alkyl, allyl, propargyl, benzyl, CH₂ CO₂ CH₃ or CH₂ CO₂ CH₂ CH₃ ; R₇ is H or CH₃ ; R₈ is Cl, C₁ -C₄ alkyl or C₁ -C₄ haloalkyl; R₉ is Cl, F, Br, CH₃, CN, OCH₃, SCH₃ or SO₂ CH₃ ; and R₁₀ is C₁ -C₄ alkyl or C₁ -C₄ haloalkyl.
 2. A compound of claim 1 wherein R and R₁ are H or halogen; and R₂ is H.
 3. The compounds of claim 1 whereinR₄ is H, C₁ -C₃ alkyl, C₁ -C₂ haloalkyl, allyl, propargyl, C₃ haloalkenyl, C₃ -C₄ alkoxycarbonylalkyl or (CH₂ CH₂ O)_(b) R₂ ; and b is 1 or
 2. 4. The compounds of claim 1 whereinR₃ is H, CN, C₁ -C₂ haloalkyl, CR₂ R₇ R₄, CR₂ R₇ CN, CH═CH₂, C.tbd.CH, COCl, COR₄, C(NOR₆)R₂, CO₂ R₄, CH₂ COR₄, CH₂ CO₂ R₄, CH₂ OC(O)R₄ or CH₂ OC(O)N(CH₃)₂ ; and R₆ is H, allyl, C₁ -C₃ alkyl or CH₂ CO₂ CH₂ CH₃.
 5. The compounds of claim 1 whereinJ is J-2, J-3, J-4, J-7, J-9, J-10, J-11, J-12 or J-15; and X and Y are O.
 6. The compound of claim 1 whereinR₉ is Cl or Br; and R₈ is CH₃.
 7. The compounds of claim 1 whereinJ is J₂ or J₁₀ ; and X¹ is O.
 8. The compounds of claim 1 whereinJ is in the 5 position; R is F or Cl and in the 4 position; and R₁ is Cl or Br and in the 2 position.
 9. The compounds of claim 1 whereinJ is in the 4 position; R is F or Cl and is in the 3 position; and R₁ is H.
 10. The compounds of claim 1 whereinJ is in the 3 position; R is F or Cl and is in the 4 position; and R₁ is H.
 11. The compounds of claim 1 whereinJ is in the 2 position; R is F or Cl and is in the 3 position; and R₁ is Cl or Br and is in the 5 position.
 12. The compounds of claim 1 whereinJ is J-2.
 13. The compounds of claim 1 whereinJ is J-10 and n is
 1. 14. The compound of claim 1 which is 2-BENZOFURAN-METHANOL-7-CHLORO-5-FLUORO-4-(2,3,4,5,6,7-HEXAHYDRO-1,3-DIOXO-1H-ISOINDOL-2-yl)-2,3-DIHYDRO-α-METHYL, ACETATE.
 15. The compound of claim 1 which is ((1,2,4)) TRIAZOLO((4,3-A)) PYRIDIN-3(2H)-ONE, 2-(5,7-DICHLORO-2,3-DIHYDRO-2-METHYL-4-BENZOFURANYL)-5,6,7,8-TETRAHYDRO.
 16. The compound of claim 1 which is 2-BENZOFURAN-CARBOXYLIC ACID-7-CHLORO-5-FLUORO-4-(2,3,4,5,6,7-HEXAHYDRO-1,3-DIOXO-1H-ISOINDOL-2-YL)-2,3-DIHYDRO-, METHYL ESTER.
 17. A composition suitable for controlling the growth of undesired vegetation which comprises an effective amount of a compound of claim 1 and at least one of the following: surfactant, solid or liquid diluent.
 18. A composition suitable for controlling the growth of undesired vegetation which comprises an effective amount of a compound of claim 2 and at least one of the following: surfactant, solid or liquid diluent.
 19. A composition suitable for controlling the growth of undesired vegetation which comprises an effective amount of a compound of claim 3 and at least one of the following: surfactant, solid or liquid diluent.
 20. A composition suitable for controlling the growth of undesired vegetation which comprises an effective amount of a compound of claim 4 and at least one of the following: surfactant, solid or liquid diluent.
 21. A composition suitable for controlling the growth of undesired vegetation which comprises an effective amount of a compound of claim 5 and at least one of the following: surfactant, solid or liquid diluent.
 22. A composition suitable for controlling the growth of undesired vegetation which comprises an effective amount of a compound of claim 6 and at least one of the following: surfactant, solid or liquid diluent.
 23. A composition suitable for controlling the growth of undesired vegetation which comprises an effective amount of a compound of claim 7 and at least one of the following: surfactant, solid or liquid diluent.
 24. A composition suitable for controlling the growth of undesired vegetation which comprises an effective amount of a compound of claim 8 and at least one of the following: surfactant, solid or liquid diluent.
 25. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a compound of claim
 1. 26. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a compound of claim
 2. 27. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a compound of claim
 3. 28. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a compound of claim
 4. 29. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a compound of claim
 5. 30. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a compound of claim
 6. 31. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a compound of claim
 7. 32. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a compound of claim
 8. 33. The method of claim 25 wherein the locus to be protected is a cereal crop and the undesired vegetation is nightshade. 